CN101394742B - Anthranilamide derivatives and their use for the control of insects and acari - Google Patents
Anthranilamide derivatives and their use for the control of insects and acari Download PDFInfo
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- 0 CC(C)(C)OC(NC1(*)CC(C)(C)*C1)=O Chemical compound CC(C)(C)OC(NC1(*)CC(C)(C)*C1)=O 0.000 description 6
- RDBGJXCKNYIQOR-CMDGGOBGSA-N C/C(/C=C)=C(/C)\NC(c1cc(C(F)(F)F)n[n]1C(N=C)=C)=O Chemical compound C/C(/C=C)=C(/C)\NC(c1cc(C(F)(F)F)n[n]1C(N=C)=C)=O RDBGJXCKNYIQOR-CMDGGOBGSA-N 0.000 description 1
- UZGJHXFEVXIGNS-RAXLEYEMSA-N CC/C(/NC(c1ccn[n]1-c1ncccc1Cl)=O)=C(\C)/C(C)=O Chemical compound CC/C(/NC(c1ccn[n]1-c1ncccc1Cl)=O)=C(\C)/C(C)=O UZGJHXFEVXIGNS-RAXLEYEMSA-N 0.000 description 1
- XGZGHRJAXIYRNB-UHFFFAOYSA-N Cc(cc(cc1C(O)=C)I)c1N Chemical compound Cc(cc(cc1C(O)=C)I)c1N XGZGHRJAXIYRNB-UHFFFAOYSA-N 0.000 description 1
- QREZLJFRFJFUQN-UHFFFAOYSA-N Cc1cc(Cl)cc(C(Cl)=C)c1N=S=O Chemical compound Cc1cc(Cl)cc(C(Cl)=C)c1N=S=O QREZLJFRFJFUQN-UHFFFAOYSA-N 0.000 description 1
- JCOPGIIMKLWNMJ-GJZGRUSLSA-N Cc1n[n](C)cc1C(Nc1c([C@H](C2)[C@@H]2C2CC2)cccc1)=O Chemical compound Cc1n[n](C)cc1C(Nc1c([C@H](C2)[C@@H]2C2CC2)cccc1)=O JCOPGIIMKLWNMJ-GJZGRUSLSA-N 0.000 description 1
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Abstract
Compounds of formula (I) wherein the substituents are as defined in claim (1), and the agrochemically acceptable salts and all stereoisomers and tautomeric forms of the compounds of formula (I) can be used as agrochemical active ingredients and can be prepared in a manner known per se.
Description
The present invention relates to new anthranilamide derivatives, the purposes of its preparation method, the composition containing these compounds, and its canonical biometric of preventing and treating insect or Acarina.
Anthranilamide derivatives with insecticidal properties are known, are described in such as WO03/015518 or WO2006/055922.Have now found that with insecticidal properties, particularly for the new anthranilamide derivatives for the member for preventing and treating insect and Acarina.The noval chemical compound is characterised by that 4- members saturated heterocyclic and the aminocarbonyl substituent of the benzyl ring are connected.
Therefore, the present invention relates to compound of formula I
Wherein
D is phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals；Or by following substituent lists-two-or trisubstd phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals：C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
Or D is group
R4、R4′、R10、R17And R19It is hydrogen, C independently of one another1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C2-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
R5、R6、R8、R11、R12、R15、R16And R18It is C independently of one another1-C6Alkyl or by following substituents are single-, two- or trisubstituted C1-C6Alkyl：Halogen, cyano group, nitro, hydroxyl, C1-C4Alkoxy, C2-C4Alkoxy carbonyl, C1-C4Alkylthio group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido or C3-C6Cycloalkyl amino；Or phenyl, 2- pyridine radicals, 3- pyridine radicals, 4- pyridine radicals；Or by following substituents are single-, two- or trisubstd phenyl, 2- pyridine radicals, 3- pyridine radicals or 4- pyridine radicals：C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1--C4Alkyl sulphonyl, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
R7、R9、R13And R14It is hydrogen, C independently of one another1-C6Alkyl, C1-C6Haloalkyl, C2-C6Alkenyl, C2-C6Haloalkenyl group, C3-C6Alkenyl or C3-C6Haloalkenyl group；
Each R1It is independently halogen, nitro, cyano group, hydroxyl, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkylsulfinyl, C1-C4Halogenated alkyl sulfonyl, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy-carbonyl oxy, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amino carbonyl oxy or C3-C6Trialkylsilkl, phenyl, benzyl or phenoxy group or by following substituents are single-, two- or trisubstd phenyl, benzyl or phenoxy group：Halogen, cyano group, nitro, halogen, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C3-C6Halogenated cycloalkyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino, C1-C6Alkyl-C3-C6Cycloalkyl amino, C2-C4Alkyl-carbonyl, C2-C6Alkoxy carbonyl, C2-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C2-C6Alkoxy-carbonyl oxy, C2-C6Alkyl amino carbonyl oxy, C3-C6Dialkyl amino carbonyl oxy or C3-C6Trialkylsilkl；
N is 0,1,2 or 3；
R2And R3Hydrogen, C each can be represented with identical or different1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl or C3-C8Cycloalkyl；Or by one or more C replaced selected from following substituents1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl or C3-C8Cycloalkyl：Halogen nitro, cyano group, hydroxyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkyl amino, C2-C4Dialkyl amido, C3-C6Cycloalkyl amino and C1-C6Alkyl-C3-C6Cycloalkyl amino；
E1And E2Oxygen or sulphur each can be represented with identical or different；
A is oxygen, sulphur, SO, SO2、S(O)p=N-R, C=N-OR36、N-R0, C=O or P (X)t-R33；
R33It is hydrogen, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Haloalkyl, C1-C6Alkoxy, hydroxyl, C3-C6Cycloalkyl, C3-C6Cycloalkyl-C1-C6Alkyl, benzyl or phenyl；Wherein phenyl and benzyl in itself can or three substitutions single-, two- by following substituents：C1-C6Alkyl, C1-C6Haloalkyl, halogen, cyano group or nitro；Or R33It is O-Na+、O-Li+Or O-K+；
R36It is hydrogen, C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C1-C6Haloalkyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C1-C6Alkoxy -C1-C6Alkyl, C1-C6Halogenated alkoxy-C1-C6Alkyl or benzyl；
X is oxygen or sulphur；
P is O or 1；
T is 0 or 1；
R34And R35Hydrogen, COOH, halogen, nitro, cyano group, hydroxyl, C each can be represented with identical or different1-C6Alkyl, C1-C6Haloalkyl, C2-C6Alkenyl, C2-C6Alkynyl, C2-C6Haloalkenyl group, C2-C6Halo alkynyl, C1-C6Alkylthio group, C1-C6Alkyl sulphinyl, C1-C6Alkyl sulphonyl, C1-C6Halogenated alkylthio, C1-C6Alkylsulfinyl, C1-C6Halogenated alkyl sulfonyl, C1-C6Alkoxy carbonyl, C1-C6Alkyl-carbonyl, C3-C6Alkyl amino-carbonyl, C3-C6Dialkyl amino carbonyl, C1-C6Alkoxy -C1-C6Alkyl, C1-C6Halogenated alkoxy-C1-C6Alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C1-C6Alkyl amino, C2-C6Dialkyl amido, C3-C6Trialkylsilkl, benzyl or phenyl；Wherein phenyl and benzyl in itself can or three substitutions single-, two- by following substituents：C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, halogen, cyano group, hydroxyl or nitro；
M is 0,1,2,3 or 4；
R is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl；Or R is the C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl：C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy, or C1-C6Halogenated alkoxy；Or R is cyano group, nitro ,-C (O) R26、-C(O)OR27、-CONR28R29、-SO2R30Or P (O) (OR31)(OR32)；
R0It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl；Or R0It is the C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl：C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy, or C1-C6Halogenated alkoxy；Or R0It is cyano group, nitro ,-C (O) R026、-C(O)R027、-CONR028R029、-SO2R030Or-P (O) (OR031)(R032)；Or R0It is phenyl or benzyl, or is selected from single-, two- following substituents or trisubstd phenyl or benzyl：C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl and C1-C4Halogenated alkyl sulfonyl；
R26And R026Hydrogen, C each can be represented with identical or different1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C1-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy carbonyl, C1-C6Alkyl-carbonyl or C1-C6Alkoxy -C1-C6Alkyl；Or the C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy carbonyl, C1-C6Alkyl-carbonyl or C1-C6Alkoxy -C1-C6Alkyl：C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy, or C1-C6Halogenated alkoxy；
R27, R28, R29, R30, R31, R32, R027, R028, R029, R030, R031And R032C each can be represented with identical or different1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl or C3-C6Halogenated cycloalkyl；Or the C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl or C1-C6Halogenated cycloalkyl：C1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy；Condition is if A is oxygen, sulphur or N-R0, wherein R0It is hydrogen, C1-C3Alkyl, C1-C3Haloalkyl, C2-C4Alkyl-carbonyl, C2-C4Halogenated alkyl carbonyl, C2-C4Alkoxy carbonyl or C1-C3Alkyl sulphonyl, then E1Or E2It is sulphur；
And agriculturally acceptable salt/isomers/diastereoisomer/enantiomter/dynamic isomer/N- oxides of these compounds.
Compound I with least one basic center can form such as acid-addition salts, such as with strong inorganic acid such as mineral acid, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or halogen acids, with strong organic carboxyl acid, such as unsubstituted or substituted C1-C4Alkyl carboxylic acid, for example it is optionally substituted by halogen, such as acetic acid, such as saturation or undersaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acid, such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or and organic sulfonic acid, such as unsubstituted or substituted C1-C4Alkyl or aryl sulfonic acid, for example, be optionally substituted by halogen, such as methanesulfonic acid or p- toluenesulfonic acid.Compound I with least one acidic-group can for example with alkali forming salt, such as mineral salt such as alkali metal or alkali salt, such as sodium salt, sylvite or magnesium salts, or with ammoniacal liquor or organic amine forming salt, the organic amine such as morpholine, piperidines, pyrrolidines, single-, two- or three-low-grade alkylamine, for example ethyl-, diethyl-, triethyl group-or dimethyl propyl amine, or single-, two- or trihydroxy-Iower-alky amine, such as single-, two- or three-monoethanolamine.Where appropriate, can also further form corresponding inner salt.Within the scope of the present invention, it is preferably the salt favourable to agriculture chemistry；However, present invention additionally comprises unfavorable salt, such as salt poisonous to honeybee and fish is applied for agriculture chemistry, the unfavorable salt is used for available salt on such as free compound I of isolated or purified or its agriculture chemistry.Due to the substantial connection between the free form and its salt form of compound of formula I, for purposes of the invention, free compound of formula I or its salt in the above and below are interpreted as including corresponding salt or free compound of formula I in due course respectively.This is equally applicable to compound I dynamic isomer and its salt.Generally, free form is preferred in all cases.
The alkyl occurred in the definition of substituent can be straight or branched, for example methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, amyl group, hexyl, heptyl and octyl group and its branched isomer.Alkoxy, alkenyl and alkynyl are derived from the alkyl.It is list-or how unsaturated that alkenyl and alkynyl, which can be,.
Halogen is typically fluorine, chlorine, bromine or iodine.Correspondingly, this is also applied for the halogen with reference to other implications, such as haloalkyl or halogenophenyl.
Haloalkyl preferably has the chain length of 1-6 carbon atom.Haloalkyl is such as methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyls, 2- fluoro ethyls, 2- chloroethyls, pentafluoroethyl group, 1,1- bis- fluoro- 2,2,2- trichloroethyls, 2,2,3,3- tetra- fluoro ethyls and 2,2,2- trichloroethyls；It is preferred that trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
Suitable haloalkenyl group is the alkenyl being mono-or polysubstituted with halogens, and halogen is fluorine, chlorine, bromine and iodine, particularly fluorine and chlorine, the fluoro- 1- methyl ethylenes of such as 2,2- bis-, 3- fluoropropene bases, chlorallylene base, 3- bromopropenyls, 2,3,3- trifluoro-propenyls, 2,3,3- tri chloropropenes base and 4,4,4- trifluoro but-2-ene -1- bases.In single-, two- by halogen or trisubstituted alkenyl, preferably with 3-5 carbon atom chain length.
Suitable halo alkynyl is the alkynyl being mono-or polysubstituted with halogens, and halogen is bromine, iodine, particularly fluorine and chlorine, such as 3- fluorine propinyl, 3- propargyl chloride bases, 3- propargyl bromide bases, 3,3,3- trifluoropropyl alkynyls and 4,4,4- trifluoro butyl- 2- alkynes -1- bases.In by halogen list-or polysubstituted alkynyl, preferably with 3-5 carbon atom chain length.
Alkoxy preferably has the chain length of 1-6 carbon atom.Alkoxy is such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and isomeric amoxy and hexyloxy；It is preferred that methoxyl group and ethyoxyl.
Alkoxy carbonyl is such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, n-butoxycarbonyl, isobutoxy carbonyl, s-butoxycarbonyl or tert-butoxycarbonyl；It is preferred that methoxycarbonyl or ethoxy carbonyl.Halogenated alkoxy preferably has the chain length of 1-6 carbon atom.Halogenated alkoxy is such as fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, 2,2,2- trifluoro ethoxies, 1,1,2,2- tetrafluoro ethyoxyl, 2- fluorine ethyoxyls, 2- chloroethoxies, 2,2- difluoroethoxies and 2,2,2- tri-chloroethoxy bases；It is preferred that difluoro-methoxy, 2- chloroethoxies and trifluoromethoxy.Alkylthio group preferably has the chain length of 1-6 carbon atom.Alkylthio group is such as methyl mercapto, ethylmercapto group, rosickyite base, isopropyisulfanyl, positive butylthio, isobutylthio, secondary butylthio or tertiary butylthio, preferably methyl mercapto and ethylmercapto group.Alkyl sulphinyl is such as methylsulfinyl, ethylsulfinyl, propylsulfenyl, isopropylsulphinyl, n-butylsulfinyl, isobutyl group sulfinyl, sec-butyl sulfinyl, terf-butylsulfinyl；It is preferred that methylsulfinyl and ethylsulfinyl.
Alkyl sulphonyl is such as methyl sulphonyl, ethylsulfonyl, sulfonyl propyl base, isopropelsulfonyl, normal-butyl sulfonyl, iso-butylsulfonyl, sec-butylsulfonyl or tert. butylsulfonyl；It is preferred that methyl sulphonyl or ethylsulfonyl.Alkyloxy-alkoxy preferably has the chain length of 1-8 carbon atom.The example of alkyloxy-alkoxy is：Methoxymethoxy, methoxy ethoxy, methoxy propoxy, (ethoxymethyl) epoxide, ethoxy ethoxy, propoxymethoxy or butoxybutoxy.Alkyl amino is such as methylamino, ethylamino, n-propyl amino, isopropylamino or isomeric butylamine.Dialkyl amido is such as dimethylamino, methylethylamine, diethylamino, n-propyl-methylamino, dibutylamino and diisopropylaminoethyl.It is preferred that alkyl amino there is the chain length of 1-4 carbon atom.Alkoxyalkyl preferably has the chain length of 1-6 carbon atom.Alkoxyalkyl is such as methoxy, methoxy ethyl, ethoxyl methyl, ethoxyethyl group, n-propoxymethyl, positive propoxy ethyl, i-propoxymethyl or isopropoxyethyl.Alkylthio alkyl preferably has the chain length of 1-8 carbon atom.Alkylthio alkyl is such as methylthiomethyl, methylmercaptoethyl, Ethylsulfanylmethyl, ethylthio-ethyl, positive rosickyite base methyl, positive rosickyite base ethyl, isopropylthiomethyl, isopropylthioethyl, Butylthiomethyl, butylthio ethyl or butylthiobutyl.Cycloalkyl preferably has 3-6 ring carbon atom, such as cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.Phenyl, in addition to as a part such as phenoxy group, benzyl, benzyloxy, benzoyl, thiophenyl, phenylalkyl, the phenoxyalkyl of substituent, can be substituted.In this case, substituent can at ortho position, ask position and/or contraposition.It is preferred that substituting group position be ortho position and contraposition relative to ring tie point.
E1And/or E2Preferably oxygen
It is preferred that compound of formula I group, wherein
a)R2It is hydrogen or C1-C4Alkyl；And/or
b)R3It is hydrogen or C1-C4Alkyl；And/or
C) D is group D1And/or
d)E2It is sulphur
Further, preferred these compound of formula I, wherein A is N- benzyls, SO or SO2, especially SO or SO2。
It is preferred that compound of formula I group represented by Formulas I a compounds
Wherein
R91It is C1-C4Alkyl or halogen, preferably chlorine, bromine or methyl；
R92It is halogen or cyano group, preferably fluorine, chlorine, bromine or cyano group；
R93It is halogen, C1-C4Haloalkyl or C1-C4Halogenated alkoxy；With
A、R34And R35There is the definition provided in above-mentioned Formulas I with m.
In preferred Formulas I or Formulas I a compounds group, A is SO, SO2、S(O)p=N-R, C=N-OR36, C=O, P (X)t-R33Or N-R0；Wherein p, t, X, R33And R36With the definition that is provided in above-mentioned Formulas I and
R0It is C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl；Or R0The C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl：C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy, or C1-C6Halogenated alkoxy；Or R0It is cyano group, nitro ,-CONR028R029Or-P (O) (OR031)(OR032), wherein R028、R029、R031And R032With the definition provided in above-mentioned Formulas I, or R0Be phenyl or benzyl or be selected from following substituents it is single-, two- or three-phenyl or benzyl of substitution：C1-C6Alkyl, C3-C6Cycloalkyl, C1-C6Haloalkyl, halogen, cyano group, C1-C4Alkoxy, C1-C4Halogenated alkoxy, C1-C4Alkylthio group, C1-C4Halogenated alkylthio, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Alkylsulfinyl and C1-C4Halogenated alkyl sulfonyl.
In further preferred Formulas I or Formulas I a compounds group, A is SO, SO2、S(O)p=N-R, C=N-OR36, C=O, P (X)t-R33Or N-R0；Wherein p, t, X, R33And R36With the definition that is provided in above-mentioned Formulas I and
R0It is C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl；Or R0It is the C replaced by following substituents1-C6Alkyl, C1-C6Haloalkyl, C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkylthio group, C1-C6Halogenated alkylthio, C1-C6Alkoxy -C1-C6Alkyl or C1-C6Halogenated alkoxy-C1-C6Alkyl：C3-C6Cycloalkyl, C3-C6Halogenated cycloalkyl, C1-C6Alkoxy, or C1-C6Halogenated alkoxy；Or R0It is cyano group, nitro ,-CONR028R029Or-P (O) (OR031)(R032), wherein R028、R029、R031And R032With the definition provided in above-mentioned Formulas I.
It should also give especially it is emphasised that these compound of formula I, wherein
e)R34It is hydrogen or C1-C4Alkyl, preferably hydrogen or methyl；And/or
f)R35It is hydrogen or C1-C4Alkyl, preferably hydrogen or methyl；And/or
G) A is oxygen, sulphur, SO, SO2, S=NR or S (O)p=NR, preferably S, SO, SO2Or S (O)p=NR wherein p are 1；Most preferably oxygen or sulphur；And/or
H) R is hydrogen, cyano group, nitro ,-C (O) R26、-C(O)OR27、-CONR28R29、-SO2R30Or-P (O) (OR31)(OR32), preferably hydrogen, cyano group ,-COOMe ,-SO2Me or-C (O) CF3And/or
i)R0It is hydrogen, cyano group, nitro ,-C (O) R026、-C(O)OR027、-CONR028R029、-SO2R030Or-P (O) (OR031)(R032), preferably hydrogen, cyano group ,-COOMe ,-SO2Me or-C (O) CF3And/or
j)R4' it is not hydrogen.
" Me " represents methyl.
In preferred compound of formula I, R26It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl or C3-C6Cycloalkyl is in preferred compound of formula I, R27、R28、R29, R30、R31And R32It is C independently of one another1-C6Alkyl or C1-C6Haloalkyl；Or by C1-C6Alkyl or C1-C6The C of haloalkyl substitution1-C6Alkyl or C1-C6Haloalkyl.
In preferred compound of formula I, R026It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl or C3-C6Cycloalkyl is in preferred compound of formula I, R027、R028、R029, R030、R031And R032It is C independently of one another1-C6Alkyl or C1-C6Haloalkyl；Or by C1-C6Alkyl or C1-C6The C of haloalkyl substitution1-C6Alkyl or C1-C6Haloalkyl.
Its dynamic isomer and/or the method for salt are similarly carried out with known method when the present invention prepares compound of formula I or be appropriate, such as in WO01/70671, WO03/016284, method described in WO03/015518 and WO04/033468.
Prepare free form in all cases or salt form compound of formula I or it is appropriate when its dynamic isomer method include, for example
A) it is preparation compound of formula I, wherein R2It is hydrogen, E1And E2It is oxygen, or where appropriate, its dynamic isomer and/or its salt,
By Formula II compound
Wherein R1, n and D there is the implication provided in Formulas I, or its dynamic isomer and/or its salt when appropriate
With formula III compound or it is appropriate when with its dynamic isomer and/or its reactant salt
Wherein A, R3、R34、R35There is the implication provided in Formulas I with m, or
B) in order to prepare compound of formula I, or its dynamic isomer and/or its salt when appropriate, by formula IV compound
Wherein R1、R2、n、E1、E2There is the implication provided in Formulas I with D；And X1It is leaving group, or its dynamic isomer and/or its salt when appropriate
With the compound of formula III or it is appropriate when with its dynamic isomer and/or its reactant salt
Wherein A, R3、R34、R35There is the implication provided in Formulas I with m, or
C) in order to prepare compound of formula I, or its dynamic isomer and/or its salt when appropriate, by Formula V compound
Wherein n, R1、R2、R3、E2、R34、R35, A and m there is the implication provided in Formulas I, or its dynamic isomer and/or its salt when appropriate
With Formula IV compound or it is appropriate when with its dynamic isomer and/or its reactant salt
X2C (=E1) D (VI),
Wherein E1There is the implication provided in Formulas I with D；And X2It is leaving group；
And/or by be in all cases free form or salt form compound of formula I or it is appropriate when its dynamic isomer change into other compound of formula I or be appropriate when its dynamic isomer, separation is according to isomer mixture obtained by method, with the isomers for isolating needs and/or by free compound of formula I or it is appropriate when its dynamic isomer change into salt, by the salt of compound of formula I or it is appropriate when its dynamic isomer change into free compound of formula I or be appropriate when its dynamic isomer or change into other salt.
Formula II compound is described in WO04/111030.Formula III and V compound are new, and are researched and developed particular for compound of formula I is prepared, therefore constitute another embodiment of the present invention.The preferred substituents of above-mentioned compound of formula I are also applied for formula III and V compounds.
In particularly preferred formula III compound
R3It is hydrogen；
R34It is hydrogen or C1-C4Alkyl, preferably hydrogen or methyl；
R35It is hydrogen, halogen, cyano group, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy -C1-C4Alkyl, C1-C4Halogenated alkoxy-C1-C4Alkyl；
A is oxygen, sulphur, SO, SO2, S=NR or S (O)p=NR, preferably S, SO, SO2Or S (O)p=NR wherein p are that 1 and wherein R is hydrogen, cyano group, nitro ,-C (O) R26、-C(O)OR27、-CONR28R29、-SO2R30Or-P (O) (OR31)(OR32), preferably hydrogen, cyano group ,-COOMe ,-SO2Me or-C (O) CF3；
M is 0,1,2,3 or 4.
In particularly preferred Formula V compound
R1It is C1-C4Alkyl, halogen, C1-C5Haloalkyl, cyano group, nitro, C1-C4Alkoxy, C1-C4- halogenated alkoxy, C1-C4Alkylthio group, C1-C4Alkyl sulphinyl, C1-C4Alkyl sulphonyl, C1-C4Halogenated alkylthio, C1-C4Alkylsulfinyl or C1-C4Halogenated alkyl sulfonyl；
R2And R3It is hydrogen；
E2It is oxygen or sulphur；
R34It is hydrogen or C1-C4Alkyl, preferably hydrogen or methyl；
R35It is hydrogen, halogen, cyano group, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxy carbonyl, C1-C4Alkoxy -C1-C4Alkyl, C1-C4Halogenated alkoxy-C1-C6Alkyl；
A is oxygen, sulphur, SO, SO2, S=NR or S (O)p=NR, preferably S, SO, SO2Or S (O)p=NR, wherein p are that 1 and wherein R is hydrogen, cyano group, nitro ,-C (O) R26、-C(O)OR27、-CONR28R29、-SO2R30Or-P (O) (OR31)(OR32), preferably hydrogen, cyano group ,-COOMe ,-SO2Me or-C (O) CF3；
M is 0,1,2,3 or 4.
N is 1,2 or 3.
Table C：It is preferred that formula III formula IIIa represent
| Cmpd No. | A | R34 | R35 |
| C1 | 0 | H | H |
| C2 | 0 | H | CH3 |
| C3 | 0 | H | CH2OCH3 |
| C4 | 0 | H | CF3 |
| C5 | 0 | 2,2-diMe | H |
| C6 | 0 | 2,2-diMe | CH3 |
| C7 | 0 | 2,2,4,4-tetraMe | H |
| C8 | 0 | 2,2,4,4-tetraMe | CH3 |
| C9 | S | H | H |
| C10 | S | H | CH3 |
| C11 | S | H | CH2OCH3 |
| C12 | S | H | CF3 |
| C13 | S | 2,2-diMe | H |
| C14 | S | 2,2-diMe | CH3 |
| C15 | S | 2,2,4,4-tetraMe | H |
| C16 | S | 2,2,4,4-tetraMe | CH3 |
| Cmpd No. | A | R34 | R35 |
| C17 | SO | H | H |
| C18 | SO | H | CH3 |
| C19 | SO | H | CH2OCH3 |
| C20 | SO | H | CF3 |
| C21 | SO | 2,2-diMe | H |
| C22 | SO | 2,2-diMe | CH3 |
| C23 | SO | 2,2,4,4-tetraMe | H |
| C24 | SO | 2,2,4,4-tetraMe | CH3 |
| C25 | SO2 | H | H |
| C26 | SO2 | H | CH3 |
| C27 | SO2 | H | CH2OCH3 |
| C28 | SO2 | H | CF3 |
| C29 | SO2 | 2,2-diMe | H |
| C30 | SO2 | 2,2-diMe | CH3 |
| C31 | SO2 | 2,2,4,4-tetraMe | H |
| C32 | SO2 | 2,2,4,4-tetraMe | CH3 |
| C33 | S(O)NH | H | H |
| C34 | S(O)NH | H | CH3 |
| C35 | S(O)NH | H | CH2OCH3 |
| C36 | S(O)NH | H | CF3 |
| C37 | S(O)NH | 2,2-diMe | H |
| C38 | S(O)NH | 2,2-diMe | CH3 |
| C39 | S(O)NH | 2,2,4,4-tetraMe | H |
| C40 | S(O)NH | 2,2,4,4-tetraMe | CH3 |
| C41 | N-CH2-C6H5 | H | H |
| C42 | N-CH2-C6H5 | H | CH3 |
| C43 | N-CH2-C6H5 | H | CH2OCH3 |
| C44 | N-CH2-C6H5 | H | CF3 |
| C45 | N-CH2-C6H5 | 2,2-diMe | H |
| C46 | N-CH2-C6H5 | 2,2-diMe | CH3 |
| C47 | N-CH2-C6H5 | 2,2,4,4-tetraMe | H |
| C48 | N-CH2-C6H5 | 2,2,4,4-tetraMe | CH3 |
Table D：It is preferred that Formula V formula Vb represent, wherein E2It is oxygen
| Cmpd No. | R91 | R92 | A | R34 | R35 |
| D1 | Me | C1 | O | H | H |
| D2 | Me | C1 | O | H | CH3 |
| D3 | Me | C1 | 0 | 2,2-diMe | H |
| D4 | Me | C1 | O | 2,2,4,4-tetraMe | H |
| D5 | Me | Br | 0 | H | H |
| D6 | Me | Br | 0 | H | CH3 |
| D7 | Me | NO2 | 0 | H | H |
| D8 | Me | NO2 | O | H | CH3 |
| D9 | Me | CN | 0 | H | H |
| D10 | Me | CN | O | H | CH3 |
| D11 | Me | CN | O | 2,2-diMe | H |
| D12 | Me | CN | 0 | 2,2,4,4-tetraMe | H |
| D13 | Me | C1 | S | H | H |
| D14 | Me | C1 | S | H | CH3 |
| D15 | Me | C1 | S | H | CH2OCH3 |
| D16 | Me | C1 | S | H | CF3 |
| D17 | Me | C1 | S | 2,2-diMe | H |
| D18 | Me | C1 | S | 2,2-diMe | CH3 |
| D19 | Me | C1 | S | 2,2,4,4-tetraMe | H |
| D20 | Me | C1 | S | 2,2,4,4-tetraMe | CH3 |
| D21 | Me | Br | S | H | H |
| D22 | Me | Br | S | H | CH3 |
| D23 | Me | NO2 | S | H | H |
| D24 | Me | NO2 | S | H | CH3 |
| D25 | Me | CN | S | H | H |
| D26 | Me | CN | S | H | CH3 |
| D27 | Me | CN | S | H | CH2OCH3 |
| D28 | Me | CN | S | H | CF3 |
| D29 | Me | CN | S | 2,2-diMe | H |
| D30 | Me | CN | S | 2,2-diMe | CH3 |
| D31 | Me | CN | S | 2,2,4,4-tetraMe | H |
| D32 | Me | CN | S | 2,2,4,4-tetraMe | CH3 |
| D33 | Me | C1 | SO | H | H |
| Cmpd No. | R91 | R92 | A | R34 | R35 |
| D34 | Me | Cl | SO | H | CH3 |
| D35 | Me | Cl | SO | H | CH2OCH3 |
| D36 | Me | Cl | SO | H | CF3 |
| D37 | Me | Cl | SO | 2,2-diMe | H |
| D38 | Me | Cl | SO | 2,2-diMe | CH3 |
| D39 | Me | Cl | SO | 2,2,4,4-tetraMe | H |
| D40 | Me | Cl | SO | 2,2,4,4-tetraMe | CH3 |
| D41 | Me | Br | SO | H | H |
| D42 | Me | Br | SO | H | CH3 |
| D43 | Me | NO2 | SO | H | H |
| D44 | Me | NO2 | SO | H | CH3 |
| D45 | Me | CN | SO | H | H |
| D46 | Me | CN | SO | H | CH3 |
| D47 | Me | CN | SO | H | CH2OCH3 |
| D48 | Me | CN | SO | H | CF3 |
| D49 | Me | CN | SO | 2,2-diMe | H |
| D50 | Me | CN | SO | 2,2-diMe | CH3 |
| D51 | Me | CN | SO | 2,2,4,4-tetraMe | H |
| D52 | Me | CN | SO | 2,2,4,4-tetraMe | CH3 |
| D53 | Me | Cl | SO2 | H | H |
| D54 | Me | Cl | SO2 | H | CH3 |
| D55 | Me | Cl | SO2 | H | CH2OCH3 |
| D56 | Me | Cl | SO2 | H | CF3 |
| D57 | Me | Cl | SO2 | 2,2-diMe | H |
| D58 | Me | Cl | SO2 | 2,2-diMe | CH3 |
| D59 | Me | Cl | SO2 | 2,2,4,4-tetraMe | H |
| D60 | Me | Cl | SO2 | 2,2,4,4-tetraMe | CH3 |
| D61 | Me | Br | SO2 | H | H |
| D62 | Me | Br | SO2 | H | CH3 |
| D63 | Me | NO2 | SO2 | H | H |
| D64 | Me | NO2 | SO2 | H | CH3 |
| D65 | Me | CN | SO2 | H | H |
| D66 | Me | CN | SO2 | H | CH3 |
| D67 | Me | CN | SO2 | H | CH2OCH3 |
| D68 | Me | CN | SO2 | H | CF3 |
| D69 | Me | CN | SO2 | 2,2-diMe | H |
| D70 | Me | CN | SO2 | 2,2-diMe | CH3 |
| D71 | Me | CN | SO2 | 2,2,4,4-tetraMe | H |
| D72 | Me | CN | SO2 | 2,2,4,4-tetraMe | CH3 |
| D73 | Me | Cl | S(O)NH | H | H |
| D74 | Me | Cl | S(O)NH | H | CH3 |
| D75 | Me | Cl | S(O)NH | H | CH2OCH3 |
| Cmpd No. | R91 | R92 | A | R34 | R35 |
| D76 | Me | Cl | S(O)NH | H | CF3 |
| D77 | Me | Cl | S(O)NH | 2,2-diMe | H |
| D78 | Me | Cl | S(O)NH | 2,2-diMe | CH3 |
| D79 | Me | Cl | S(O)NH | 2,2,4,4-tetraMe | H |
| D80 | Me | Cl | S(O)NH | 2,2,4,4-tetraMe | CH3 |
| D81 | Me | Br | S(O)NH | H | H |
| D82 | Me | Br | S(O)NH | H | CH3 |
| D83 | Me | NO2 | S(O)NH | H | H |
| D84 | Me | NO2 | S(O)NH | H | CH3 |
| D85 | Me | CN | S(O)NH | H | H |
| D86 | Me | CN | S(O)NH | H | CH3 |
| D87 | Me | CN | S(O)NH | H | CH2OCH3 |
| D88 | Me | CN | S(O)NH | H | CF3 |
| D89 | Me | CN | S(O)NH | 2,2-diMe | H |
| D90 | Me | CN | S(O)NH | 2,2-diMe | CH3 |
| D91 | Me | CN | S(O)NH | 2,2,4,4-tetraMe | H |
| D92 | Me | CN | S(O)NH | 2,2,4,4-tetraMe | CH3 |
Table G：It is preferred that Formula V formula Vb represent, wherein E2It is sulphur, lists compound G1-G92, wherein R91, R92, A, R34And R35With the implication given by table D D1-D92 rows.
The physical data of table C, D and G formula III a and Vb compound：
| Compound number | Fusing point | 1H-NMR |
| C10 | Liquid | CDCl3：3.25 (d, 2H), 3.04 (d, 2H), 1.78 (s, 2H), 1.53 (s, 3H). |
| C42 | Oil | CDCl3：7.2 (m, 5H), 3.62 (s, 2H), 3.27 (d, 2H), 2.88 (d, 2H), 1.68 (bs, 2H), 1.4 (s, 3H). |
| C9, is used as hydrobromate | 186-190℃ | d6-DMSO：8.23 (br s, 3H), 4.52 (m, 1H), 3.47 (m, 2H), 3.18 (m, 2H). |
| C26, is used as trifluoroacetate | 208-210℃ | d6-DMSO：8.82 (br s, 3H), 4.56 (d, 2H), 4.29 (d, 2H), 1.68 (s, 3H). |
| C13 | Oil | CDCl3：3.83 (dd, 1H), 3.19 (t, 1H), 2.95 (t, 1H), 1.63 (br |
| Compound number | Fusing point | 1H-NMR |
| S, 2H), 1.50 (s, 3H), 1.42 (s, 3H). | ||
| D54 | 79-82℃ | CDCl3：7.20 (s, 1H), 7.12 (s, 1H), 6.52 (s, 1H), 5.58 (brs, 2H), 4.64 (d, 2H), 4.15 (d, 2H), 2.13 (s, 3H), 1.87 (s, 3H). |
| D14 | 92-94℃ | CDCl3：7.14 (s, 1H), 7.10 (s, 1H), 6.09 (s, 1H), 5.57 (brs, 2H), 3.90 (d, 2H), 3.03 (d, 2H), 2.14 (s, 3H), 1.83 (s, 3H). |
R2It is the group of the Formula V compound of hydrogen, Formula V a compounds can be prepared for example similar to method described in WO2001/070671.
Formula V a compounds can also be prepared by making Formula X I be reacted with formula III compound in the presence of alkali and atent solvent.
Wherein n, R1、R3、E2、R34、R35, A and m there is the implication gone out given in Formulas I；And X1It is leaving group (such as chlorine, bromine), or, where appropriate, its dynamic isomer and/or salt.
Suitable alkali is, for example, N (C2H5)3, DBU, DBN or imidazoles.It is preferred that solvent be tetrahydrofuran, dioxane, glyme, ethyl acetate or toluene.The temperature at 0 DEG C to 100 DEG C is reacted, preferably+15 DEG C to about+30 DEG C, is particularly carried out at ambient temperature.Other methods of formula V compounds are described in PCT/EP2006/003504.
Especially it should be emphasized that the group of the Formula V compound represented by Formula V b compounds
Wherein
R91It is C1-C4Alkyl or halogen, preferably chlorine, bromine or methyl；
R92It is halogen or cyano group, preferably fluorine, chlorine, bromine or cyano group；And
E2、A、R34、R35There is the implication gone out given in Formulas I with m.
Wherein E2Be oxygen Formula V/Va/Vb acid amides by using commercially available thio conversion reagent, such as phosphorus pentasulfide and Lawesson reagents, such as similar to X.Fontrodona et al., Synthesis, 2001, (13), 2021-27, is easily transformed into wherein E2It is Formula V/Va/Vb of sulphur thioamides.
Formula X I, wherein especially X1Those the Formula X Is for being chlorine can be with, such as similar to J.Garin et al., Tetrahedron Letters, and 1991,32,3263-64 prepare.
Formula III compound either known in the literature, or can be similarly prepared according to known method.
Wherein R3It is the group of the formula III compound of hydrogen, formula III a compounds can be prepared for example via reduction or reduction amination or via acid treatment as described above, or can also be similarly prepared according to known method.
The group of the compound of formula I represented by Formulas I b compounds
Wherein n, R1、R2、R3、D、E1、E2、R34、R35, m and R there is the implication provided in Formulas I, for example in scheme a), b) or c) in the conditions of similarity described in compound of formula I under prepare, wherein scheme a), b) or c) in Formulas I, III and V group A by wherein p be 1 S (O)p=NR groups are replaced.
Alternatively, Formulas I b compounds, or, if appropriate, its dynamic isomer and/or salt, are in all cases free form or salt form, for example can be by Formula VII compound according to known method and step (H.Okamura, C.Bolm, Org.Lett.2004,6,1305；H.Okamura, C.Bolm, Chem.Lett.2004,33,482；D.Leca, K.Song, M.Amatore, L.Fensterbank, E.
M.Malacria, Chem.Eur.J.2004,10,906) or preparation described below
Wherein n, R1、R2、R3、D、E1、E2、R34、R35There is the implication gone out given in Formulas I with m, and q is 0 or 1.
The group A of compound of formula I or formula III compound, wherein Formulas I and III is by S (O) that wherein p is 1p=NR groups are replaced, such as by Formula VII compound
Wherein n, R1、R2、R3、D、E1、E2、R34、R35It is 0 or 1 to have the implication gone out given in Formulas I and q with m, or is prepared by Formula VIII compound according to known step
R3, R34, R35It is 0 or 1 (flow 1 to have the implication gone out given in Formulas I and q with m：Q=0：Step A, then B；Q=1：Step B, see, e.g. M.Reggelin, C.Zur, Synthesis, 2000,1).Formula III, V and VIII compounds are novel, are developed exclusively for compound of formula I is prepared, therefore constitute the further object of the present invention.
Alternatively, compound of formula I or formula III compound, wherein the group A of Formulas I and III are by S (O) that middle p is 1p=NR groups are replaced, such as by Formula IX compound
Wherein n, R1、R2、R3、D、E1、E2、R34、R35, m and R have the implication gone out given in Formulas I, or prepared by Formula X compound according to known method
Wherein R3、R34、R35, m and R there is the implication (scheme 1 gone out given in Formulas I, step A ') its compound of formula IX or Formula X compound be by such as Formula VII compound (q=0), or Formula VIII compound (q=0) is according to known method, it is prepared by such as scheme 1, method described step B '.
For sulfide is converted into sulfoxide or sulfilimine is converted into for sulfoximine (scheme 1, step A or A '), classical oxidant is KMnO4、mCPBA、NaIO4/RuO2、H2O2, potassium hydrogen peroxymonosulfate.For sulfoxide is converted into sulfoximine or sulfide is converted into for sulfilimine (scheme 1, step B or B '), classical reagent is NaN3/H2SO4, O- mesitylene sulfonyl chlorides azanol (MSH), or metal catalytic method, such as RN3/FeCl2, PhI=N-R/CuOTf, PhI=N-R/Cu (OTf)2, PhI=N-R/CuPF6、PHI(OAc)2/R-NH2/MgO/Ru2(OAc)4Or oxaziridine (such as 3- (4- cvano-phenyls)-oxaziridine -2- carboxylates).
Detailed preparation condition available for synthesis type Ib compounds (sulfoximine) is provided in WO2006/061200.
It is equally applicable to for content described in compound of formula I I dynamic isomer and/or salt described on dynamic isomer and/or the starting material of its salt in the above and below.
Reaction is carried out in a way known described in above and below, for example it is being not present or generally in the case where there is suitable solvent or diluent or its mixture, as needed cooling, at room temperature or heating, for example in about -80 DEG C of boiling point temperature ranges to reactant mixture, it is preferred that from about -20 DEG C to about+150 DEG C, and if necessary in closed container, under decompression, normal pressure or high pressure, carry out under inert gas atmosphere and/or in anhydrous conditions.Particularly advantageous reaction condition is found in embodiment.
Unless otherwise indicated, the raw material of its dynamic isomer is known or can for example prepared by method known per se according to data described below when being used for of mentioning in the above and below prepares compound of formula I in all cases for free form or salt form or be appropriate.
Reactant can react in the presence of base.Suitable for promoting HX2The example of the alkali of disengaging is alkali metal or alkaline earth metal hydroxide, alkali metal or alkaline earth metal hydride, alkali metal or alkaline earth metal amides, alkali metal or alkaline-earth alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonate, alkali metal or alkaline-earth metal dialkylamides or alkali metal or alkaline-earth metal alkylsilyl-amides, alkyl amine, Alkylenediamine class, the saturation or unsaturation ring alkyl amine, basic heterocycles, ammonium hydroxide and carbocyclic ring amine of free or N- alkylations.The example that can be mentioned that is sodium hydroxide, sodium hydride, Sodamide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, hydrofining, lithium diisopropylamine, double (trimethyl silyl) potassamides, calcium hydride, triethylamine, diisopropyl ethyl amine, triethylenediamine, cyclohexylamine, N- cyclohexyl-N, N- dimethyl amines, N, N- diethylanilines, pyridine, 4- (N, N- dimethylaminos) pyridine, quinine pyridine, N-methylmorpholine, benzyl trimethylammonium hydroxide and 1, carbon -7- the alkene (DBU) of 8- diazabicylos [5.4.0] 11.
Reactant can directly react to each other, i.e., need not add solvent or diluent.However, in most cases, addition atent solvent or diluent or its mixture are usually favourable.If reaction is carried out in the presence of base, the alkali being excessively used such as triethylamine, pyridine, N-methylmorpholine or N, N- diethylaniline can also act as solvent or diluent.
Reaction is carried out advantageously in about -80 DEG C to about+140 DEG C temperature ranges, preferably approximately -30 DEG C to about+100 DEG C, in most cases in room temperature in the range of about+80 DEG C.
By replacing initial compounds I one or more substituents with other substituents of the present invention in a usual manner, compound I can be changed into another compound I in a way known.
According to the selection of to reaction condition and in all cases applicable raw material, a substituent can be replaced with another substituent of the present invention for example only in a reactions steps, or with other substituents of the present invention multiple substituents are replaced in same step.
The salt of compound of formula I can be prepared in a way known.Obtain, can be obtained with the salt of alkali formation by using suitable alkali or the processing of suitable ion exchange reagent thus, for example compound I acid-addition salts can be handled by using suitable sour or suitable ion exchange reagent.
The salt of compound of formula I can change into free compound of formula I in a usual manner, acid-addition salts are for example handled by using suitable alkali compounds or suitable ion exchange reagent, are for example handled with the salt of alkali formation by using suitable sour or suitable ion exchange reagent.
The salt of compound of formula I can change into other salt of compound of formula I in a manner known per se, acid-addition salts are for example changed into other acid-addition salts, for example, the salt in suitable solvent with a kind of sour suitable metal salt such as sodium salt, barium salt or silver salt such as silver acetate processing inorganic acid such as hydrochloric acid can be passed through, the inorganic salts formed in the solvent are insoluble such as silver chlorate, therefore are precipitated out from reactant mixture.
, can in a free form or salt form is obtained with the compound of formula I into salt performance according to method or reaction condition.
The configuration of the number of the asymmetric carbon atom according to present in molecule, absolute and relative configuration and/or the non-aromatic double bond according to present in molecule, compound of formula I in all cases for free form or salt form and it is appropriate when its dynamic isomer using in the form of one of possible isomers or the presence of its mixture can be used as, for example in the form of pure isomer, such as enantiomer and/or diastereomer, or it is used as isomer mixture, such as enantiomeric mixture, such as racemate, non-enantiomer mixture or racemate mixture；The present invention relates to pure isomer and all possible isomer mixture, and all should so it understand in the above and below, even if stereochemical details are not referred to clearly in all cases.
The free form or the non-enantiomer mixture or racemic mixture of the compound of formula I of salt form that can be obtained according to the raw material and method of selection, pure diastereomer or racemate can be separated into known manner according to the physical chemical differences of each composition, for example, pass through fractional crystallization, distillation and/or chromatography.
The enantiomeric mixture that can be obtained in a similar manner such as racemate can be split as optical antipode by known method, for example by being recrystallized from optically-active solvent, pass through the chromatographic isolation on chiral sorbent, high performance liquid chromatography (HPLC) for example on cellulose acetate, by suitable microorganism, by using specific immobilised enzymes digestion, by forming inclusion compound, for example using chiral crown ether, in this case a kind of enantiomer is complexed, or by changing into diastereomeric salt, for example pass through basic termini product racemate and optically-active acid reaction, such as carboxylic acid, such as camphoric acid, tartaric acid or malic acid, or sulfonic acid, such as camphorsulfonic acid, with separation obtainable non-enantiomer mixture in this way, fractional crystallization for example by being carried out based on its different solubility, produce diastereomer, therefrom dissociated desired enantiomer by the effect of suitable reagent such as alkaline reagent.
The pure diastereomer or enantiomer of the present invention can not only be obtained by separating suitable isomer mixture, it can also be obtained by commonly known cis-selectivity or enantioselective synthesis method, for example, implement the method for the present invention by using suitable stereochemical raw material.
In all cases, if there is individual compound more effectively isomers in different bioactivity, separation or synthetic biology to be favourable, such as enantiomer or diastereomer or isomer mixture, such as mixture of enantiomers or non-enantiomer mixture.
The compounds of this invention in all cases for free form or salt form and it is appropriate when its dynamic isomer can also obtain hydrate forms if necessary and/or comprising other solvents, may for example have been used for crystallizing the solvent of the compound existed in solid form.
The compound of the present invention is the active component for having prevention and/or therapeutic value in field of pest control, even under low rate of application, it has very favorable biocidal scope and is resistant to well by warm blooded species, fish and plant.The animal pests of the active component of the present invention not only to all or individual development stages conventional sensitivities, and antagonism animal pest, the canonical biometric of such as insect or Acarina are effective.The active component of the present invention kills insect or acaricidal activity and can directly displayed, shown with the Mortality of insect for occurring immediately or occurring for example during cast off a skin merely through a period of time, or show that excellent activity is equivalent to elimination rate (death rate) at least 50 to 60% indirectly for example to reduce spawning and/or incubation rate.
The example of above-mentioned animal pest is：
Acarina (Acarina), for example
Acarus siro (Acarus siro),Citrus aceria (Aceria sheldoni),Steinman pin thorn goitre mite (Aculus schlechtendali),Amblyomma (Amblyomma spp.),Hidden beak ant belongs to (Argas spp.),Boophilus (Boophilus spp.),Short whisker Acarapis (Brevipalpus spp.),Lucerne place tongue mite (Bryobia praetiosa),Calipitrimerus spp.,Trombiculid (Chorioptes spp.),Dermanyssus gallinae (Dermanyssus gallinae),Eotetranychus carpini (Eotetranychus carpini),Eriophyes (Eriophyes spp.),Hyalommaspp (Hyalomma spp.),Hard ant category (Ixodes spp.),Meadow unguiculus mite (Olygonychus pratensis),Beak tick belongs to (Ornithodoros spp.),Red spider belongs to (Panonychus spp.),Citrus rust mite (Phyllocoptruta oleivora),Polyphagotarsonemus latus Banks (Polyphagotarsonemuslatus),Overworked mite belongs to (Psoroptes spp.),Rh (Rhipicephalus spp.),Root mite belongs to (Rhizoglyphus spp.),Sarcoptesspp (Sarcoptes spp.),Line mite belongs to (Tarsonemus spp.) and tetranychus telarius category (Tetranychus spp.)；
Anoplura (Anoplura), for example
Haematopinus (Haematopinus spp.), Linognathus (Linognathus spp.), Pediculus (Pediculus spp.), Pemphigus (Pemphigus spp.) and Phylloxera spp (Phylloxera spp.)；
Coleoptera (Coleoptera), for example
Click beetle belongs to (Agriotes spp.),Anthonomus spp belongs to (Anthonomus spp.),Atomaria linearis (Atomaria linearis),Chaetocnema tibialis (Chaetocnema tibialis),Banana root weevil belongs to (Cosmopolites spp.),Curculio (Curculio spp.),Khapra beetle belongs to (Dermestes spp.),The chrysomelid category (Diabrotica spp.) of bar,Plant ladybug category (Epilachna spp.),Eremnus spp.,Colorado potato bug (Leptinotarsadecemlineata),Lissorhoptrus oryzophilus Kuschel belongs to (Lissorhoptrus spp.),Gill cockchafer belongs to (Melolontha spp.),Saw-toothed grain beetle belongs to (Orycaephilus spp.),Otiorhynchus spp (Otiorhynchus spp.),Spot is as category (Phlyctinus spp.),Rutelian belongs to (Popillia spp.),Phyllotreta (Psylliodes spp.),Dynamic root moth category (Rhizopertha spp.),Scarabeidae (Scarabeidae),Sitophilus (Sitophilusspp.),Gelechiid belongs to (Sitotroga spp.),Tenebrio (Tenebriom spp.),Intend paddy temperature category (Tribolium spp.) and khapra beetle category (Trogoderma spp.)；
Diptera (Diptera), for example
Aedes (Aedes spp.),Jowar awns mosquito (Antherigonas occata),Garden march fly (Bibio hortulanus),Calliphora (Calliphora erythrocephala),Anastrepha (Ceratitis spp.),Carysomyia (Chrysomyia spp.),Culex (Culexspp.),Cuterbrid belongs to (Cuterebra spp.),Anastrepha (Dacus spp.),Drosophila yellow gorilla (Drosophila melanogaster),Fannia (Fannia spp.),Horse botfly belongs to (Gastrophilus spp.),Glossina (Glossina spp.),Hypoderma (Hypodermaspp.),Hippobosca (Hyppobosca spp.),Hippelates (Liriomysa spp.),Lucilia (Lucilia spp.),The black Hippelates of dried bean curd (Melanagromyza spp.),Fly belongs to (Musca ssp.),Oestrus (Oestrus spp.),Cecidomyiia belongs to (Orseolia spp.),Sweden's wheat stem chloropid fly (Oscinella frit),Kmangold fly (Pegomyia hyoscyami),Spring wheat fly belongs to (Phorbia spp.),Apple trypetid (Rhagoletis pomonella),Gill fungus fly belongs to (Sciara spp.),Genus Stomoxys (Stomoxys spp.),Gadfly (Tabanus spp.),Tanniaspp. with big uranotaenia (Tipula spp.)；
Heteroptera (Heteroptera), for example
Cimex (Cimex spp.), Distantiella theobroma (Distantiella theobroma), red stinkbug belongs to (Dysdercus spp.), America stinkbug category (Euchistus spp.), brown scutteleerid belongs to (Eurygaster spp.), Leptocorisa spp belongs to (Leptocorisa spp.), Bemisia spp (Nezaraspp.), lace bug belongs to (Piesma spp.), red abdomen Reduvius (Rhodnius spp.), Sahlbergella singularis (Sahlbergella singularis), scotinophora lurida belongs to (Scotinophara spp.) and Triatoma (Triatoma spp.)；
Homoptera (Homoptera), for example
Continuous confused lice (Aleurothrixus floccosus),Aleyrodes (Aleyrodesbrassicae),Circle helmet a red-spotted lizard category (Aonidiella spp.),Aphidiadae (Aphididae),Aphis (Aphis spp.),Aspidiotus belongs to (Aspidiotus spp.),Sweet potato whitefly (Bemisiatabaci),Lecanium belongs to (Ceroplaster spp.),Chrysomphalus aonidium (Chrysomphalusaonidium),Dictyospermum scale (Chrysomphalus dictyospermi),Coccushesperidum (Coccushesperidum),Empoasca spp belongs to (Empoasca spp.),Eriosoma lanigerum (Eriosomalarigerum),Erythema leafhopper belongs to (Erythroneura spp.),Gascardia spp.,Small brown-back rice plant-hopper belongs to (Laodelphax spp.),East ball lecanium (Lecanium corni),Lepidosaphes belongs to (Lepidosaphes spp.),Macrosiphus spp.,Knurl volume Aphis (Myzusspp.),Rice green leafhopper belongs to (Nephotettix spp.),Brown paddy plant hopper belongs to (Nilaparvataspp.),Parlatoria (Parlatoria spp.),Pemphigus (Pemphigus spp.),Stern line mealybug belongs to (Planococcus spp.),White peach scale belongs to (Pseudaulacaspis spp.),Mealybug belongs to (Pseudococcus spp.),Leaf Pediculus (Psylla ssp.),Cotton a red-spotted lizard (Pulvinaria aethiopica),Aspidiotus belongs to (Quadraspidiotus spp.),Pipe of hanging belongs to (Rhopalosiphum spp.),Helmet a red-spotted lizard belongs to (Saissetia spp.),Leafhopper belongs to (Scaphoideus spp.),Green bugs belongs to (Schizaphis spp.),Paddy net Aphis (Sitobion spp.),Greenhouse whitefly (Trialeurodes vaporariorum),Wood louse (Trioza erytreae) and Unaspis citri (Unaspis citri)；
Hymenoptera (Hymenoptera), for example
Ci Qieye mosquitos Acromyrmex, Myrmecina (Atta spp.), stem honeybee belongs to (Cephusspp.), tenthredinidae (Diprion spp.), Diprionidae (Diprionidae), Gilpinia polytoma (Gilpinia polytoma), tenthredinidae (Hoplocampa spp.), field ant category (Lasiusspp.), ant belongs to (Monomorium pharaonis), Neodiprion spp belongs to (Neodiprion spp), Solenopsis (Solenopsis spp.) and Vespa (Vespa ssp.)；
Isoptera (Isoptera), for example
Flat thorn mealybug category (Reticulitemes spp)；
Lepidoptera (Lepidoptera), for example
Acleris spp belongs to (Acleris spp.),Steinernema belongs to (Adoxophyes spp.),Clearwing moth belongs to (Aegeria spp.),Agrotis (Agrotis spp.),Cotton leaf ripple noctuid (Alabama argillaceae),Amylois spp.,Anticarsia (Anticarsiagemmatalis),Archips spp (Archips spp),Argyrotaenia belongs to (Argyrotaeniaspp.),Noctua (Autographa spp.),Corn pattern noctuid (Busseola fusca),Meal moth (Cadra cautella),Small heart-eating peach worm (Carposina nipponensis),Straw borer spp (Chilo spp.),Roll up moth category (Choristoneura spp.),Grape codling moth (Clysia ambiguella) (Clysia ambiguella),The vertical volume snout moth's larva category (Cnaphalocrocis spp.) of rice,Leaf roller belongs to (Cnephasia spp.),Cochylisspp belongs to (Cochylis spp.),Casebearer moth (Coleophoraspp.),General non-fine hair snout moth's larva (Crocidolomia binotalis),Cryptophlebia leucotreta (Cryptophlebia leucotreta),Beans steinernema belongs to (Cydia spp.),Different Crambus Fabricius (Diatraea spp.),Diparopsis castanea (Diparopsis castanea),Earias (Earias spp.),Meal moth belongs to (Ephestia spp.),Preserved egg steinernema belongs to (Eucosmaspp.),Ligustrum fine tortricidae (Eupoecili aambiguella),Euproctis (Euproctisspp.),Cutworm belongs to (Euxoa spp.),Small leaf volume belongs to (Grapholita spp.),The wide wing steinernema of cloud and mist (Hedya nubiferana),Genus heliothis (Heliothis spp.),Hellula undalis (Hellula undalis),Fall webworms (Hyphantria cunea),Tomato pinworm moth (Keiferia lycopersicella),Pear leaf blister moth (Leucoptera scitella),Thin moth category (Lithocollethis spp.),Flower wing steinernema (Lobesia botrana),Euproctis (Lymantria spp.),Lyonetiaspp (Lyonetia spp.),Malacosoma (Malacosoma spp.),Lopper worm (Mamestra brassicae),Maduca sexta (Manduca sexta),Winter geometrid moth belongs to (Operophtera spp.),Corn borer (OstriniaNubilalis),Super steinernema belongs to (Pammene spp.),Brown epiblema (Pandemis spp.),Small noctuid (Panolis flammea),Pink bollworm (Pectinophoragossypiella),Potato tuberworm (Phthorimaea operculella),Cabbage butterfly (Pieris rapae),Pieris spp (Pieris spp.),Diamondback moth (Plutellaxylostella),Yponomeuta (Prays spp.),Yellow rice borer belongs to (Scirpophaga spp.),Pink rice borer belongs to (Sesamia spp.),Long hair volume moth category (Sparganothis spp.),Spodoptera (Spodoptera spp.),Clearwing moth belongs to (Synanthedon spp.),Band moth category (Thaumetopoea spp.),Leaf roller belongs to (Tortrix spp.),Cabbage looper (Trichoplusia ni) and Yponomeuta (Yponomeuta spp.)；
Mallophaga (Mallophaga), for example
Damalinia (Damalinea spp.) and Trichodectes (Trichodectes spp.)；
Orthoptera (Orthoptera), for example
Blattaria category (Blatta spp.), Blatella (Blattella spp.), Gryllotalpa spp (Gryllotalpa spp.), Ma get La blattarias (Leucophaea maderae), migratory locusts category (Locusta spp.), Periplaneta (Periplaneta ssp.) and grasshopper category (Schistocercaspp.)；
Corrodentia (Psocoptera), for example
Powder corrodent belongs to (Liposcelis spp.)；
Siphonaptera (Siphonaptera), for example
Ceratophyllus (Ceratophyllus spp.), Ctenocephalus (Ctenocephalidesspp.) and Xanthopsyllacheopis (Xenopsylla cheopis)；
Thysanoptera (Thysanoptera), for example
Flower thrips category (Frankliniella spp.), Hercinothrips spp category (Hercinothrips spp.), Scirtothrips aurantii (Scirtothrips aurantii), Taeniothrips (Taeniothripsspp.), pale brown thrips (Thrips palmi) and cotton thrips (Thrips tabaci)；
Thysanoptera (Thysanura), for example
Silverfiss (Lepisma saccharina).
The active component of the present invention can be used for preventing and treating; suppress or eliminate the plant especially occurred from agricultural, gardening and forestry; the insect of the above-mentioned type especially on useful plant and ornamental plant or on its organ such as fruit, flower, leaf, stem, stem tuber or root; in some cases, or even the organ of the useful plants formed later can be protected from the infringement of these insects.
Suitable Target crops are to be particularly, cereal, such as wheat, barley, rye, oat, rice, corn or jowar；Beet, such as sugar beet and fodder beet；Fruit, such as a kind of fruit, such as apple, pear, etc., drupe or soft fruit, such as apple, pears, plum, peach, apricot, cherry or berry, such as strawberry, raspberry or blackberry, blueberry；Legume, such as Kidney bean, lens, pea or soybean；Oilseed plant, such as rape, leaf mustard, opium poppy, olive, sunflower, coconut, castor-oil plant, cocoa bean or peanut；Muskmelon platymiscium, such as pumpkin, cucumber or muskmelon；Fibre plant, such as cotton, flax, hemp or jute；Citrus fruit, such as orange, lemon, grape fruit or orange；Vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or bell pepper；Lauraceae, such as avocado, Chinese cassia tree or camphor；And tobacco；Nut；Coffee；Eggplant, sugarcane, tea, pepper；Liana, hop, plantago, latex plant and ornamental plant.
The active component of the present invention is particularly suitable for use in preventing and treating the bean aphid in cotton, vegetables, corn, rice and soybean crops, and band spot cucumber is chrysomelid, tobacco budworm, black peach aphid, diamondback moth and Spodoptera littoralis.The active component of the present invention is also particularly suitable preventing and treating lopper worm and belonged to (preferably in vegetables), codling moth (preferably in apple), leafhopper (Empoasca) is (preferably in vegetables, in vineyard), thin instep is chrysomelid to be belonged to (preferably in potato) and striped rice borer (preferably in rice).
Term " crop " is interpreted as also including because conventional breeding methods or gene engineering method make its herbicide-tolerant such as Brominal or multiclass herbicide (such as HPPD inhibitor, ALS inhibitor, such as primisulfuronmethyl, prosulfuron and trifloxysulfuron, EPSPS (5- enol-pyrovyl-shikimate -3- phosphate synthases) inhibitor, GS (glutamine synthelase) inhibitor) crop.Having made the example of the crop of its resistance to imidazolone type such as imazamox by conventional breeding methods (mutagenesis) is
Summer oil fruit (rape (canola)).The example of the crop of herbicide-resistant or classes of herbicides is allowed to by gene engineering method includes resistance glyphosate and the corn of glufosinate-resistant, and the kind can be according to trade name
WithCommercially.
Term " crop " is interpreted as also including that the crop of one or more selectively acting toxin can be synthesized by using recombinant DNA technology conversion, and the toxin comes from those bacteriums that toxin produces bacterium, particularly bacillus as known.
It can be included by the toxin of the Expressed in Transgenic Plant, such as insect-killing protein for example comes from the insect-killing protein of bacillus subtilis or Japanese beetle bacillus；Or come from the insect-killing protein of bacillus thuringiensis, such as delta-endotoxin, such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative insecticidal proteins matter (VIP), such as VIP1, VIP2, VIP3 or VIP3A；Or the insect-killing protein of bacteria paragenesis nematode, such as Photorhabdus or Xenorhabdus, such as luminous light rod bacterium, Xenorhabdus nematophilus；The toxin produced by animal, such as scorpion toxin, spider toxin, wasp toxin and other insect-specific neurotoxins；By mycetogenetic toxin, such as strepto- verticillium toxin；Phytolectin, such as pisum sativum agglutinin, barley lectin element or GNA；Pleurotus Ostreatus；Protease inhibitors, such as trypsin inhibitor, serpin, potato storage protein (patatin), cystatin, antipain；Ribosome inactivating protein (RIP), such as ricin, corn-RIP, abrin, Luffin, Saponaria officinalis toxin protein or red bryony toxalbumin；Steroid metabolism enzyme, such as 3- hydroxy steroids oxidizing ferment, ecdysteroid-UDP- glycosyls-transferase, cholesterol oxidase, moulting hormone inhibitor, HMG-COA- reductases, ion channel blocking agent, such as sodium channel or calcium channel blocker, JH esterase, diuretic hormone acceptor, stilbene synthase, bibenzyl synthases, chitinase and dextranase.
Within the scope of the present invention, delta-endotoxin such as CryIA (b), CryIA (c), CryIF, CryIF (a2), CryIIA (b), CryIIIA, CryIIIB (b1) or Cry9c, or vegetative insecticidal proteins (VIP), such as VIP1, VIP2, VIP3 or VIP3A are interpreted as obviously also including mixing toxin, truncate (truncated) toxin and modified toxins.Mixing toxin is (see such as WO02/15701) produced by the Combination nova restructuring in the difference in functionality area of those protein.The CryIA (b) of truncated toxins such as truncation is known.For modified toxins, one or more amino acid of naturally occurring toxin are replaced.In this amino acid replacement, preferably non-naturally occurring protease recognition sequence is inserted in toxin, such as in the case of CryIIIA055, a kind of cathepsin-D- recognition sequences are inserted into CryIIIA toxin (see WO03/018810).
Above-mentioned toxin or the example for the genetically modified plants that can synthesize above-mentioned toxin are disclosed in such as EP-A-0374753, WO93/07278, WO95/34656, EP-A-0427529, EP-A-451878 and WO03/052073.
The preparation method of above-mentioned genetically modified plants is generally known to those skilled in the art, is described in for example above-mentioned publication.CryI- types DNA and its preparation are known in such as WO
95/34656, EP-A-0367474, EP-A-0401979 and WO90/13651.
Contained toxin causes plant to have tolerance to harmful insect in genetically modified plants.The insect may reside in any classification of insect group, but especially be that typically in what is found in beetle (coleoptera), dipteran (Diptera) and butterfly (Lepidoptera).
The genetically modified plants of gene containing one or more coded insect-killing agent resistances and the one or more toxin of expression are known, and some of them are commercially available.The example of the plant is：(corn variety expresses CryIA (b) toxin)；YieldGard
(corn variety expresses CryIIIB (b1) toxin)；YieldGard
(corn variety, expression CryIA (b) and CryIIIB (b1) toxin)；
(corn variety expresses Cry9 (c) toxin)；Herculex
(the enzyme glufosinate-ammonium N- acetyltransferases (PAT) of corn variety, expression CryIF (a2) toxin and acquisition to herbicide glufosinate ammonium drug resistance)；NuCOTN
(cotton variety expresses CryIA (c) toxin)；Bollgard
(cotton variety expresses CryIA (c) toxin)；
(cotton variety, expression CryIA (c) and CryIIA (b) toxin)；(cotton variety, expression VIP toxin)；NewLeaf (Potato Cultivars, expression CryIIIA toxin)；NatureGard Agrisure GTAdvantage (GA21 glyphosate tolerants character), Agrisure CB Advantage (Bt11 corn borers (CB) character) and Protecta.
Other examples of the genetically modified crops are：
1.Bt11 corns, from Syngenta Seeds SAS, Cheminde1 ' Hobit27, F-31790St.Sauveur, France, registration number C/FR/96/05/10.Genetically altered maize, CryIA (b) toxin truncated by transgene expression makes it to resist the invasion and attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides).Bt11 corns also transgene expression PAT enzymes are to obtain the tolerance to herbicide glufosinate ammonium.
2.Bt176 corns, from Syngenta Seeds SAS, Chemin de1 ' Hobit27, F-31790St.Sauveur, France, registration number C/FR/96/05/10.Genetically altered maize, makes it to resist the invasion and attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgene expression CryIA (b) toxin.Bt176 corns also transgene expression PAT enzymes are to obtain the tolerance to herbicide glufosinate ammonium.
3.MIR604 corns, from Syngenta Seeds SAS, Chemin de l ' Hobit27, F-31790St.Sauveur, France, registration number C/FR/96/05/10.Corn of the CryIIIA toxin being modified by transgene expression with insect-resistant.This toxin is the Cry3A055 by inserting cathepsin-D-protease recognition sequence and modification.The preparation of the transgenic corns is described in WO03/018810.
4.MON863 corns, from Monsanto Europe S.A.270-272Avenuede Tervuren, B-1150Brussels, Belgium, registration number C/DE/02/9.MON863 expresses CryIIIB (b1) toxin, and resistant to some coleopterons.
The cottons of 5.IPC 531, from Monsanto Europe S.A.270-272Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6.1507 corns, from Pioneer Overseas Corporation, AvenueTedesco, 7B-1160Brussels, Belgium, registration number C/NL/00/10.Genetically altered corn, marking protein CrylF is to obtain resistance and PAT protein to some lepidopterous insects to obtain the tolerance to herbicide glufosinate ammonium.
7.NK603 × MON810 corns, from Monsanto Europe S.A.270-272Avenue de Tervuren, B-1150Brussels, Belgium, registration number C/GB/02/M3/03.Hybridized by genetically altered kind NK603 and MON810, be made up of the hybrid corn variety of conventional breeding.The CP4EPSPS protein that the expression of NK603 × MON810 corn genes is obtained by Agrobacterium strains CP4, is allowed to herbicide-resistant Roundup
(containing glyphosate), and CryIA (b) toxin obtained by B. thuringiensis subspecies, it is allowed to resistance to some lepidopterous insects, including European corn borer.
The genetically modified crops of insect-resistant plants are also described in BATS (Zentrum f ü rBiosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse13,4058 Basel, Switzerland) Report 2003, (http://bats.ch)。
Term " crop " is interpreted as also including converting the crop for making it antipathogen for example so-called ＂ pathogenesis related protein ＂ (PRPs be shown in such as EP-A-0392225) of the synthesis with selectively acting by using recombinant DNA technology.The antipathogen and the example for the genetically modified plants that can synthesize the antipathogen are known in such as EP-A-0392225, WO95/33818 and EP-A-O353191.The manufacture method of the genetically modified plants is generally known to those skilled in the art, and is described in for example above-mentioned publication.
Such as ion channel blocking agent, the blocking agent of such as sodium and calcium channel, such as viral KP1, KP4 or KP6 toxin can be included by the antipathogen of the Expressed in Transgenic Plant；Stilbene synthase；Bibenzyl synthases；Chitinase；Dextranase；So-called " pathogenesis related protein " (PRPs；See such as EP-A-0392225)；The albumen or polypeptide factor (so-called " Plant Genes Conferring Resistance To Pathogens ", as described in WO03/000906) being related in the antipathogen produced by microorganism such as peptide antibiotic or heterocyclic antibiotics (see such as WO95/33818) or plant pathogen defence.
The other application field of the present composition is protection Stored Product and storeroom; and protect raw material; such as timber, textile, floor or building, and health field is additionally operable to, human body, domestic animal and agricultural animals is especially protected to resist the insect of the type.
In health field, composition of the invention is effective to ectoparasite such as hardware tick, software tick, itch mite, trombiculid, flies (sting to sting and lick and sting), parasitic screwworm, louse, head louse, bird lice and flea.
The example of this kind of parasite is：
Anoplura (Anoplurida)：Blind pediculus (Haematopinus spp.), Linognathus (Linognathus spp.), Pediculus (Pediculus spp.) and Pthirus (Phtirusspp.), pipe Pediculus (Solenopotes spp.).
Mallophaga stings lice (Mallophagida)：Filoplume Pediculus (Tr imenopon spp.), Menopon spp., huge Trichodectes (Trinoton spp.), Bovicola (Bovicolaspp.), Werneckiella spp., Lepikentron spp., Damalinia (Damalinaspp.), Trichodectes (Trichodectes spp.) and Felicola (Felicola spp.).
Diptera (Diptera) and the short beak of Nematocera (Nematocerina) and right angle are as suborder (Brachycerina),Such as Aedes (Aedes spp.),Spot Anopheles (Anophelesspp.),Culex (Culex spp.),Simulium (Simulium spp.),The true buffalo gnat of all woolen (Eusimulium spp.),Sand fly (Phlebotomus spp.),Lutzomyia (Lutzomyiaspp.),Storehouse midge (Culicoides spp.),Spot horsefly (Chrysops spp.),Knurl horsefly (Hybomitra spp),Atylotus (Atylotus spp.),Gadfly (Tabanus spp.),Chrysozona (Haematopota spp.),Philipomyia spp.,Honeybee Hippobosca (Braulaspp.),Fly belongs to (Musca spp.),Hydrotaea (Hydrotaea spp.),Sting fly (Stomoxys spp.),Haematobia (Haematobia spp.),Fly does not belong to (Morelliaspp.),Latrine fly (Fannia spp.),Glossina (Glossina spp.),Calliphora (Calliphora spp.),Lucilia (Lucilia spp.),Carysomyia (Chrysomyiaspp.),Wohlfahrtia (Wohlfahrtia spp.),Sarcophaga (Sarcophaga spp.),Oestrus (Oestrus spp.),Torsalo (Hypoderma spp.),Gasterophilus (Gasterophilus spp.),Hippoboscid (Hippobosca spp.),Deer Lipoptena (Lipoptera spp.) and Melophagus (Melophagus spp.).
Siphonaptera (Siphonapterida), for example, flea category (Pulex spp.), Ctenocephalus (Ctenocephalides spp.), mouse flea (Xenopsylla spp.), and c. leaf flea (Ceratophyllus spp.).
Heteroptera (Heteropterida), for example, Cimex (Cimex spp.), triatoma sanguisuga category (Triatoma spp.), Rhodnius (Rhodnius spp.), and Panstrongylus (Panstrongylus spp.).
Blattaria (Blattarida), such as oriental cockroach (Blattaorientalis), American cockroach (Periplaneta americana), Groton bug (Blattela germanica) and brown belt Lian category (Supella spp.).
Mite subclass (Acarida) and metaspiracle mesh (Metastigmata) and mesostigma mesh (Mesostigmata), for example, hidden beak tick belongs to (Argas spp.), beak tick belongs to (Ornithodorusspp.), ear tick (Otobius spp.), hard tick (Ixodes spp.), Amblyomma (Amblyomma spp.), Boophilus (Boophilus spp.), Dermacentor (Dermacentorspp.), Haemolaelaps (Haemophysalis spp.), glass eye tick (Hyalomma spp.), carrapato belongs to (Rhipicephalus spp.), Dermanyssus gallinae (Dermanyssus spp.), auspicious vertical tapeworm (Raillietia spp.), Pneumonyssus (Pneumonyssus spp.), Sternostoma (Sternostoma spp.) and Varroa (Varroa spp.).
Spoke mite suborder (Actinedida) (preceding valve suborder (Prostigmata)) and Sarcoptiformes (Acaridida (Astigmata)), such as mite category (Acarapis spp.), Cheyletiella (Cheyletiella spp.), tampan tick belongs to (Ornithocheyletia spp.), Myobia (Myobia spp.), itch mite (Psorergates spp.), compacted mite belongs to (Demodexspp.), sandmite belongs to (Trombicula spp.), rabbit yak mite belongs to (Listrophorus spp.), Tyroglyphus (Acarus spp.), junket mite belongs to (Tyrophagus spp.), thermophilic wooden mite (Caloglyphus spp.), Hypodectes spp., wing clothing mite belongs to (Pterolichusspp.), overworked mite belongs to (Psoroptes spp.), skin Psoroptes (Chorioptes spp.), ear leprosy mite belongs to (Otodectes spp.), Sarcoptesspp (Sarcoptes spp.), scab mite belongs to (Notoedres spp.), lump mite belongs to (Knemidocoptes spp., ), Cytodites (Cytodites spp.) and Laminosioptes (Laminosioptes spp.).
The present composition applies also for invasion and attack of the protection materials from insect, such as timber, textile, plastics, adhesive, glue, paint, paper and card, leather, floor and building.
Therefore, the invention further relates to composition pesticide, as emulsifiable concentrate, suspension stoste, can Direct spraying or dilution solution, paintable paste, diluting emulsion, soluble powder, dispersible powder, wettable powder, pulvis, granule or the capsule of polymeric material encapsulating, wherein containing at least one inventive compound, and to dosage form selection to adapt to the target to be applied and main environment.
In these compositions, active component is used in a pure form, for example with the solid active agent of specific particle diameter, or the conven-tional adjuvants preferably with least one preparation in industrial, such as bulking agent, such as solvent or solid carrier, or as surface active cpd (surfactant) is used together.
The example of suitable solvent is：Unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably C8-C12Alkylbenzene part, such as xylene mixture, alkylated naphthalene or tetrahydronaphthalene, aliphatic or alicyclic hydro carbons, such as alkane or hexamethylene, alcohols, such as ethanol, propyl alcohol or butanol, glycol and its ether and esters, such as propane diols, dipropylene glycol, ethylene glycol or ethylene glycol monomethyl or single ethylether, ketone, such as cyclohexanone, isophorone or diacetone alcohol, intensive polar solvent class, such as NMP, dimethyl sulfoxide or N, dinethylformamide, water, unepoxidized or epoxidised vegetable oil, for example unepoxidized or epoxidised rapeseed oil, castor oil, coconut oil or soybean oil, and silicone oil.
It is usually the natural minerals of crushing for the solid carrier in such as pulvis and dispersible powder, such as calcite, talcum, kaolin, montmorillonite or Attagel.In order to improve its physical property, the silicic acid of polymolecularity or the adsorbability polymer of polymolecularity can also be added.Suitable granulated adsorbent carrier is cellular type, for example float stone, brickbat, sepiolite or bentonite；Suitable non-adsorptive support is calcite or sand.In addition it is possible to use the plant residue of substantial amounts of inorganic or organic particulate material, especially dolomite or crushing.
According to the property of active component to be prepared, suitable surface active cpd is nonionic, cation and/or anion surfactant, or the surfactant mixture with good emulsifiability, dispersive property and wet performance.Surfactant listed below should be regarded solely as example；Other surfaces activating agent that many formulation arts are commonly used and suitable for the present invention is described in pertinent literature.
The polyglycol ether derivative of suitable nonionic surfactant particularly aliphatic series or alicyclic alcohol, saturation or unrighted acid or alkyl phenol, described derivative contains about 3 to about 30 ethylene glycol ether groups and has about 8 to about 20 carbon atoms in (ring) aliphatic hydrocarbon moieties, or has about 6 to about 18 carbon atoms in the moieties of alkyl phenol.Other desirably PEOs contain about 20 to about 250 ethylene glycol ether groups and about 10 to about 100 propylene glycol ether groups with polypropylene glycol, vinyl diaminourea polypropylene glycol and the water-soluble addition thing of the alkyl polypropylene glycol containing 1 to about 10 carbon atom in alkyl chain, wherein addition product.Above-claimed cpd usually contains 1 to about 5 ethylene glycol unit/propylene glycol units.The example that can be mentioned that is nonylphenoxy polyethoxy ethanol, castor oil polyglycol ether, PPOX/polyethylene oxide adducts, tributyl phenoxypolyethoxy ethanols, polyethylene glycol and octylphenoxy polyethoxy ethanol.The fatty acid ester of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate are also suitable.
Cationic surfactant particularly quaternary ammonium salt, the quaternary ammonium salt usually contains at least one alkyl group containing about 8 to about 22 carbon atoms as substituent, and is used as (non-halo or halo) the low alkyl or low hydroxy alkyl or benzyl group of other substituents.The salt is preferably halide, Methylsulfate or ethyl sulfuric acid salt form.The example is stearyl trimethyl ammonium chloride and benzyl two (2- chloroethyls) ethyl phosphonium bromide ammonium.
The example of suitable anion surfactant is the surface active cpd of water-soluble soaps and water-soluble synthesis.The example of suitable soaps is the sodium salt or sylvite of the alkali metal salt, alkali salt or (be unsubstituted or be substituted) ammonium salt of the aliphatic acid containing about 10 to about 22 carbon atoms, such as oleic acid or stearic sodium salt or sylvite or the natural acid mixture that can be obtained from such as coconut oil or pine tar；It can be mentioned that also have aliphatic acid methyl taurate.However, more generally using the surfactant of synthesis, especially fatty acid sulfonate, fatty acid sulfates, the benzimidizole derivatives or alkylaryl sulfonates of sulfonation.Fatty acid sulfonate and fatty acid sulfates generally exist with alkali metal, alkaline-earth metal or (be unsubstituted or be substituted) ammonium salt; and generally there is the alkyl group containing about 8 to about 22 carbon atoms, alkyl is also understood as including the moieties of carboxyl groups；It can be mentioned that example be lignin sulfonic acid, dodecyl sulphate or the fatty alcohol sulphuric acid admixture obtained by natural acid sodium salt or calcium salt.The salt of salt and fatty alcohol sulfonic acid/ethylene oxide adduct of this group also including sulfuric ester.Sulphonated benzimidazole derivative preferably comprises 2 sulfonyls and 1 fatty acid group containing about 8 to about 22 carbon atoms.The example of alkylaryl sulfonates is DBSA, the sodium salt of dibutyl naphthalenesulfonic acid or naphthalene sulfonic acids/formaldehyde condensation products, calcium salt or tri ethanol ammonium salt.Furthermore, it is also possible to use be suitable phosphate, such as the salt or phosphatide of the phosphate of p- nonyl phenol/(4-14) ethylene oxide adduct.
Composition usually contains 0.1 to 99%, especially 0.1 to 95% active component and 1 to 99.9%, especially 5 to 99.9% at least one solid or liquid adjuvants, 0 to 25%, especially 0.1 to 20% (percentage is by weight) of usual composition is probably surfactant.However, composition in a concentrated form is preferred commercially available prod, end user will have significantly lower activity component concentration usually using dilution preparation, the dilution preparation.It is preferred that composition especially as follows constitute (%=percentage by weights)：
Emulsifiable concentrate：
Active component：1 to 95%, preferably 5 to 20%
Surfactant：1 to 30%, preferably 10 to 20%
Solvent：5 to 98%, preferably 70 to 85%
Pulvis：
Active component：0.1 to 10%, preferably 0.1 to 1%
Solid carrier：99.9 to 90%, preferably 99.9 to 99%
Concentrate colloidal suspending agent：
Active component：5 to 75%, preferably 10 to 50%
Water：94 to 24%, preferably 88 to 30%
Surfactant：1 to 40%, preferably 2 to 30%
Wettable powder：
Active component：0.5 to 90%, preferably 1 to 80%
Surfactant：0.5 to 20%, preferably 1 to 15%
Solid carrier：5 to 99%, preferably 15 to 98%
Granule：
Active component：0.5 to 30%, preferably 3 to 15%
Solid carrier：99.5 to 70%, preferably 97 to 85%
Composition can also contain other solids or liquid adjuvants, such as stabilizer is for example unepoxidized or epoxidised vegetable oil (such as epoxidised coconut oil, rapeseed oil or soya-bean oil), defoamer such as silicone oil, preservative, viscosity modifier, adhesive and/or tackifier, fertilizer or the other active components for obtaining special-effect, such as bactericide, fungicide, nematicide, plant activator, invertebrate poison or herbicide.
The present composition is prepared in inherently known method, in the case of auxiliary agent is lacked, for example prepared by crushing, sieving and/or extrusion solid active component, in the case of there is at least one auxiliary agent, for example, prepared by mixing and/or grinding closely mixture of active principles with auxiliary agent (a variety of auxiliary agents).The purposes that the preparation method and compound I of these compositions prepare these compositions is also subject of the present invention.
The application process of composition, that is the method for the insect of control the above-mentioned type, the method for example sprayed, be atomized, dust, coat, dress seed, broadcast sowing or pour into a mould-according to the expected purpose of main environment selects-and the purposes of insect of composition for preventing and controlling the above-mentioned type be other themes of the invention.Typical concentration rate is 0.1 to 1000ppm, preferably 0.1 to 500ppm active component.The amount of application of per hectare is usually 1 to 2000g active ingredient per hectares, especially 10 to 1000g/ha, preferably 10 to 600g/ha.
In crop protection field, preferred application process is the blade (foliage applying) for being applied to plant, can select application times and amount of application with being matched by the danger of the pest attacks.Alternatively, plant location can be impregnated with by using fluid composition or mixture of active principles is mixed into plant location in solid form, soil is for example mixed into, for example in granular form (soil application), active component is reached plant by root system (systemic action).For rice crop, the granule is applied to the rice field basined irrigation with can measuring.
The present composition is also applied to the invasion and attack for protecting plant propagation material from the insect of the above-mentioned type, such as seed, such as fruit, stem tuber or benevolence, or rice shoot.Propagating materials can be handled with said composition before planting：Seed can be for example handled prior to seeding.Alternatively, benevolence can also be impregnated by using fluid composition or composition is applied to by benevolence (coating) by coating solid composition layer.When planting propagating materials, said composition can also be applied to plantation place, for example, kind of a furrow are applied to during sowing.The processing method of these plant propagation materials and so processed plant propagation material are also subject of the present invention.
Prepare embodiment
Following embodiments are intended to illustrate the present invention, show preferred compound of formula I.Free valence bond represents methyl.
Embodiment P1：Prepare compound T13.1.2：
Step 1：Prepare 2- methyl -2- nitro-1,3-propylene glycol xylene sulfonates：
Similar to F.I.Carroll, J.Org.Chem.1969,34,466-8：
At -15 ° to -20 DEG C, to 2- methyl -2- nitros -1, ammediol (80g, 0.592mol) with triethylamine (131.8g, ether (800ml) solution of toluene sulfochloride (225.7g, 1.184mol) is added in ether (250ml) solution 1.303mol).Gained suspension is stirred 1 hour at 0 DEG C, is then stirred at room temperature 18 hours.The reactant mixture is filtered, gained solid residue is dissolved in ethyl acetate twice, the suspension is filtered in stirring again.The ethyl acetate layer of the merging is evaporated to dryness, first crude product (175.8g) is obtained.The ether filtrate water (2x) and salt water washing, dry (Na2SO4), partial concentration.Filter the suspension and obtain other 15.0g products.The solid crude product (190.8g, 73%) is directly used in next step, without being further purified.
Step 2：Prepare 3- methyl-3-nitros-Thietane：
Similar to K.K.Andersen et al., J.Org.Chem.1978,43,3827-34：
By DMSO (130ml) solution vulcanized sodium (Na of 2- methyl -2- nitro-1,3-propylene glycols xylene sulfonates (product of step 1) (17g, 38.3mmol)2S·xH2O32-38%, 11.92g ,~53.5mmol) processing, and the mixture is stirred 2 hours 90 DEG C (110 DEG C of bath temperature).Reactant mixture is cooled down, is poured into water, uses Et2O is extracted.The organic layer of merging water (2x) and salt water washing, dry (Na2SO4), filtering and concentration.Liquid crude product (3.52g, 69%) is directly used in next step, without being further purified.
Step 3：Prepare 3- amino -3- methyl-Thietane：
To 3- methyl-3-nitros-Thietane (product of step 2) (3.52g, ammonium chloride (1.55g 26.4mmol) is added in the solution of ethanol (100ml) and water (50ml), 29.0mmol), then iron powder (14.0g is added, 250.7mmol), the mixture is heated to reflux 1 hour.Reactant mixture is cooled down, is filtered by Hyflo, residue is washed with ether and dichloromethane, the filtrate that the lower careful concentration of decompression merges, light yellow liquid product (0.66g, 24%) is directly used in next step, without being further purified.
1H-NMR(CDCl3)：(s, the 3H) of 3.25 (d, J=9.3Hz, 2H), 3.04 (d, J=9.8Hz, 2H), 1.78 (s, 2H), 1.53
Step 4：Prepare (2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (3- methyl-Thietane -3- bases carbamoyl)-phenyl]-acid amides)：
To the chloro- 2- of 6- [1- (3- chloro-2-pyridyls) -3- (trifluoromethyl) -1H- pyrazoles -5- bases] -8- methyl -4H-3,1- benzoxazin-4-ones (1.13g, 2.56mmol) (according to WO02/48115, it is prepared by embodiment 2D) tetrahydrofuran (15ml) solution in add 3- amino -3- methyl-Thietane (product of step 3) (0.66g, 6.40mmol), the compound is heated at 50 DEG C 48 hours, be then refluxed for 12 hours.Reactant mixture is cooled down, is then poured into water, is extracted with ethyl acetate, merges organic layer, with water and salt water washing, (Na is dried2SO4), filter and concentrate.Pass through the purification by flash chromatography crude product (ethyl acetate/hexane 1：2) 560mg (40%) title compound, is obtained, is white solid, m.p.238-241 DEG C.
1H-NMR(CDCl3)：10.19 (s, 1H), 8.46 (d, 1H), 7.88 (d, 1H), 7.69 (s, 1H), 7.41 (dd, 1H), 7.10 (s, 2H), 6.39 (s, 1H), 3.63 (d, 2H), 2.98 (d, 2H), 2.09 (s, 3H), 1.68 (s, 3H)；MS (electron spray ES+)：544,546 (M+H)+.
Step 5：Prepare compound T13.1.2 (2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acid [4- chloro-2-methyls -6- (3- methyl isophthalic acids, the λ of 1- dioxies -16- Thietane -3- bases carbamoyl)-phenyl]-acid amides)：
To 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (3- methyl-Thietane -3- bases the carbamoyl)-phenyl]-acid amides (product of step 4; 150mg; m- chlorine benzylhydroperoxide (143mg is added in dichloromethane (10ml) solution 0.275mmol); 0.579mmol), the compound is stirred at room temperature 1 hour.The reactant mixture partial concentration is dissolved in ethyl acetate, organic layer saturation Na2CO3The aqueous solution (3x) and salt water washing, dry (Na2SO4), filtering and concentration.The crude product is purified by flash chromatography (ethyl acetate) and obtains 78mg (49%) title compound T13.1.2, is white solid, m.p.168-171 DEG C.
1H-NMR(CDCl3)：9.61 (s, 1H), 8.48 (d, 1H), 7.90 (d, 1H), 7.42 (dd, 1H), 7.33 (s, 1H), 7.25-7.22 (2xs, 2H), 6.72 (s, 1H), 4.38 (d, 2H), 4.09 (d, 2H), 2.14 (s, 3H), 1.75 (s, 3H)；MS (electron spray ES+)：576,578 (M+H)+.
Each compound T44.1.2 of embodiment P2. systems：
Step 1：Prepare the triflate of 2- methyl -2- nitro-1,3-propylene glycols two：
To trifluoromethanesulfanhydride anhydride (16.5ml, 2- methyl -2- nitros -1 are added in chloroform (50ml) solution 0.1mol), ammediol (6.75g, 0.05mol) with pyridine (8.85ml, the solution of chloroform (50ml) 0.11mol), during addition, with outside cooling to ensure temperature as 0 DEG C to 5 DEG C.Addition is finished, and removes cooling bath, and the reaction 18 hours is stirred at room temperature.Reactant mixture is transferred in separatory funnel, is washed with water.Dry (Na2SO4) organic layer, filter, be evaporated to dryness.By chromatogram purification crude product, with 4：1 hexane：Ethyl acetate mixture is used as eluant, eluent.Obtain solid product, 50-52 DEG C of fusing point.
Step 2：Prepare 3- methyl-3-nitro-N- benzyl azetidines：
By 2- methyl -2- nitros -1, the triflate of ammediol two [product of step 1] (4.0g, acetonitrile (70ml) solution 10mmol) is cooled to 0 DEG C~5 DEG C, add N- ethyldiisopropylamines (3.23g, 25mmol), then benzyl amine (1.60g, 15mmol) is added, mixture is stirred at 80 DEG C 12 hours.Reactant mixture is cooled down, is concentrated under reduced pressure, is dissolved in ethyl acetate and is transferred to separatory funnel.Then it is used into water (2x) and salt water washing, dries (Na2SO4), filtering and concentration.Liquid crude product is directly used in next step, without being further purified.Use 3：1 hexane：Ethyl acetate mixture is as eluant, eluent, by the chromatogram purification crude product, obtains oil product.1H-NMR(CDCl3)：7.3 (m, 5H), 3.75 (d, 2H), 3.68 (s, 2H), 3.42 (d, 2H), 1.88 (s, 3H).
Step 3：Prepare 3- amino -3- methyl-N-benzyl azetidines：
Solution of the 3- methyl-3-nitro-N- benzyls azetidines [product of step 2] (3.9g, 18.9mmol) in ethyl acetate (370ml) and 5% acetic acid (370ml) is heated to backflow.Iron powder (5.25g, 94.1mmol) is added portionwise within every 5 minutes.After addition is finished, the reactant mixture is heated to reflux 6 hours.Reactant mixture is cooled down, is filtered by Hyflo, residue is washed with ethyl acetate.Filtrate is transferred in separatory funnel, organic layer is separated, and discard.Water layer is handled with 30%NaOH solution under ice-cooling, provides about 11 pH.Then dichloromethane is added, the mixture is stirred vigorously at room temperature 10 minutes.The mixture is filtered by Hyflo.Filtrate is transferred in separatory funnel, organic layer is separated, (Na is dried2SO4), filtering and concentration.Oily crude product (2.30g, 69%) is directly used in next step, without being further purified.1H-NMR(CDCl3)：7.2 (m, 5H), 3.62 (s, 2H), 3.27 (d, 2H), 2.88 (d, 2H), 1.68 (bs, 2H), 1.4 (s, 3H).
Step 4：Prepare compound T44.1.2 (2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (3- methyl-N-benzyl azetidine -3- bases carbamoyl)-phenyl]-acid amides)：
To the chloro- 2- of 6- [1- (3- chloro-2-pyridyls) -3- (trifluoromethyl) -1H- pyrazoles -5- bases] -8- methyl -4H-3,1- benzoxazin-4-ones (353mg, 0.8mmol) [according to WO02/48115, embodiment 2D prepare] tetrahydrofuran (10ml) in add 3- amino -3- methyl-N-benzyls azetidine [product of step 3] (176mg, 0.8mmol), the mixture is stirred at room temperature 18 hours.The reactant mixture is concentrated, crude product is purified by flash chromatography (ethyl acetate), obtains 250mg (45%) title compound T44.1.2, be white solid, m.p.127-130 DEG C.
1H-NMR(CDCl3)：10.4 (s, 1H), 8.4 (d, 1H), 7.85 (d, 1H), 7.75 (s, 1H), 7.4 (dd, 1H), 7.26 (m, 5H), 7.1 (d, 2H), 6.5 (s, 1H), 3.5 (s, 2H), 3.35 (d, 2H), 3.07 (d, 2H), 2.1 (s, 3H), 1.57 (s, 3H).
Embodiment P3：Prepare compound T9.1.1：
Step 1：Prepare N- (tertbutyloxycarbonyl) -3- Thietane amine：
With vulcanized sodium (Na2S·xH2O32-38%, 16.82g,~75.4mmol) processing N- (tertbutyloxycarbonyl) -2- amino -1, ammediol bis-mesylate is [according to E.Benoist et al., it is prepared by Synthesis1998, (8), 1113-1118] (25g, ethanol (375ml) solution 72.0mmol), the mixture is stirred 45 minutes at a temperature of 50 DEG C (60 DEG C of bath temperature).Reactant mixture is cooled down, is concentrated under reduced pressure, and solid residue is poured into water, Et is used2O is extracted, the organic layer salt water washing of merging, dries (Na2SO4), filtering and concentration.Solid crude product (12.6g, 92%) is directly used in next step, without being further purified.
Step 2：Prepare 3- thia ring butylamine hydrobromates：
By 5.7M HBr acetic acid solution (11.0ml, in ether (250ml) solution for 62.7mmol) being added drop-wise to N- (the tertbutyloxycarbonyl) -3- thia rings butylamine [product of step 1] (9.17g, 48.5mmol) cooled down at -20 DEG C.The mixture is stirred at -20 DEG C 10 minutes.Cooling bath is removed, at room temperature stirring reaction 3 hours.Gained white suspension is filtered, the residue is washed with ether, first product (6.0g) is obtained.Ether filtrate is concentrated, and the residue is placed under same reaction condition again, post processing obtains other 1.3g products.Solid crude product (7.3g, 89%), fusing point is 186-190 DEG C, next step is directly used in, without being further purified.
1H-NMR(d6-DMSO)：8.23 (br s, 3H), 4.52 (m, 1H), 3.47 (m, 2H), 3.18 (m, 2H).
Step 3：Prepare 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (Thietane -3- bases carbamoyl)-phenyl]-acid amides：
To the chloro- 2- of 6- [1- (3- chloro-2-pyridyls) -3- (trifluoromethyl) -1H- pyrazoles -5- bases] -8- methyl -4H-3,1- benzoxazin-4-ones (500mg, 1.13mmol) [according to WO02/48115, it is prepared by embodiment 2D] tetrahydrofuran (10ml) solution in add triethylamine (0.4ml, 2.87mmol) with 3- thia ring butylamine hydrobromate [product of step 2] (250mg, 1.47mmol), and by the mixture heated overnight at reflux.Compound of reaction is cooled down, is poured into water, is extracted with ethyl acetate, the organic layer water and salt water washing of merging dry (Na2SO4), filtering and concentration.Pass through flash chromatography (ethyl acetate/hexane 1：2) crude product is purified, the 250mg that attains the Way (41%) title compound, is white solid.
1H-NMR(CDCl3)：9.94 (s, 1H), 8.48 (d, 1H), 7.88 (d, 1H), 7.42 (dd, 1H), 7.29 (s, 2H), 7.24 (s, 1H), 6.53 (d, 1H), 5.31 (m, 1H), 3.41 (m, 2H), 3.33 (m, 2H), 2.18 (s, 3H)；MS (electron spray ES+)：530,532 (M+H)+。
Step 4：Prepare compound T9.1.1 (2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (λ of 1- oxygen -14- Thietane -3- bases carbamoyl)-phenyl]-acid amides)：
At 0 DEG C; to 2- (the chloro- pyridine -2- bases of 3-) -5- trifluoromethyl -2H- pyrazoles -3- carboxylic acids [4- chloro-2-methyls -6- (Thietane -3- bases carbamoyl)-phenyl]-acid amides [product of step 3] (200mg; dichloromethane (10ml) 0.377mmol) is added dropwise to dichloromethane (2ml) solution of m- chloro- benzylhydroperoxide (93mg, 0.377mmol).0 DEG C stirring 40 minutes after, it is necessary to the m- chloro- benzylhydroperoxide of other 10mg with complete reaction.Reactant mixture saturation NaHCO3Aqueous solution processing, and extracted with dichloromethane, the organic layer salt water washing of merging, dry (Na2SO4), filtering and concentration.Crude product is purified by flash chromatography (ethyl acetate), is obtained 50mg (24%) title compound T9.1.1, is white solid, m.p.241-244 DEG C of (main diastereoisomer is referred to as T9.1.1 diastereoisomer A)
1H-NMR(d6-DMSO)：10.38 (s, 1H), 8.91 (d, 1H), 8.54 (d, 1H), 8.23 (d, 1H), 7.75 (s, 1H), 7.67 (dd, 1H), 7.52 (s, 1H), 7.42 (s, 1H), 4.22 (m, 1H), 3.95 (m, 2H), 3.16 (m, 2H), 2.20 (s, 3H)；MS (electron spray ES+)：546,548 (M+H)+.
Embodiment P4：Prepare compound T13.1.22：
Step 1：Prepare 1,1- dioxy -3- methyl -3- thia ring butylamine trifluoroacetates：
At 0 DEG C, with trifluoroacetic acid (13ml) processing N- (tertbutyloxycarbonyl) -1,1- dioxy -3- methyl -3- Thietanes amine [is similar to embodiment P3, step 1 and embodiment P1, it is prepared by step 5] (1.7g, dichloromethane (20ml) solution 7.2mmol), and the reactant mixture is stirred at room temperature overnight.The mixture is concentrated under decompression, solid residue is suspended in ether, stirred, filtered and dry.Solid crude product (1.4g, 78%), 208-210 DEG C of fusing point is directly used in next step, without being further purified.1H-NMR(d6-DMSO)：8.82 (brs, 3H), 4.56 (d, 2H), 4.29 (d, 2H), 1.68 (s, 3H).
Step 2：Prepare the chloro- 3- methyl -2- sulfonamido chlorobenzoyl chlorides of 5-
Similar to J.Garin et al., Tetrahed ron Lett.1991,32,3263-3264：
To the chloro- 3- methyl-benzoic acids (18.5g of 2- amino -5-, thionyl chloride (36ml is added in toluene (200ml) suspension 100mmol), 500mmol), and the mixture is heated to backflow, stir at such a temperature until the gas quickly separated out is stopped.The lower concentration resulting solution of decompression, high vacuum dry obtains solid residue.Solid crude product (23.7g, 95%), is directly used in next step, without being further purified.
1H-NMR(CDCl3)：8.07 (d, 1H), 7.56 (d, 1H), 2.30 (s, 3H).
Step 3：Prepare 2- amino -5- chloro- 3- methyl-N- (3- methyl isophthalic acids, the λ of 1- dioxies -16- Thietane -3- bases)-benzamide
To the 1 of 0-5 DEG C of cooling, 1- dioxies -3- methyl -3- thia ring butylamine trifluoroacetate [product of step 1] (598mg, 2.40mmol) with triethylamine (0.836ml, tetrahydrofuran (4ml) solution of the chloro- 3- methyl -2- sulfonamidos chlorobenzoyl chlorides of 5- [product of step 2] (600mg, 2.4mmol) is added in tetrahydrofuran (6ml) solution 6.00mmol).Stirring reaction mixture is stayed overnight at room temperature, is then poured into water.After being extracted with ethyl acetate, merge organic layer, use salt water washing, dry (Na2SO4), filtering and concentration.Pass through silica gel column chromatography (ethyl acetate/hexane 1：4) crude product is purified, title benzamide [table D compounds D54] (410mg, 56%) is obtained, is white solid, 79-82 DEG C of fusing point.
1H-NMR(CDCl3)：7.20 (s, 1H), 7.12 (s, 1H), 6.52 (s, 1H), 5.58 (br s, 2H), 4.64 (d, 2H), 4.15 (d, 2H), 2.13 (s, 3H), 1.87 (s, 3H)；MS (electron spray ES+)：303,305 ((M+H)+)。
Step 4：Prepare compound T13.1.22 (2- (the chloro- pyridine -2- bases of 3-) -5- (2,2,2- trifluoro-ethoxy) -2H- pyrazoles -3- carboxylic acid [4- chloro-2-methyls -6- (3- methyl isophthalic acids, the λ of 1- dioxies -16- Thietane -3- bases carbamoyl)-phenyl]-acid amides)
To the chloro- 3- methyl-N- of 2- amino -5- (the 3- methyl isophthalic acids, the λ of 1- dioxies -1 in 0-5 DEG C of cooling6- Thietane -3- bases)-benzamide [product of step 3] (340mg, 2- (the chloro- pyridine -2- bases of 3-) -5- (2 is added in tetrahydrofuran (6ml) solution 1.12mmol), 2,2- trifluoro-ethoxies) -2H- pyrazoles -3- carbonyls chlorine (1.12mmol, 1eq.) tetrahydrofuran (4ml) solution.Mixture is stirred at room temperature to stay overnight, vacuum evaporating solvent.Pass through silica gel column chromatography (ethyl acetate/hexane gradient 1：4→1：1) crude product is purified, title bisamide T13.1.22 (279mg, 41%) is obtained, is white solid, fusing point>250℃.
1H-NMR(CDCl3)：10.05 (s, 1H), 8.83 (s, 1H), 8.45 (d, 1H), 7.85 (d, 1H), 7.42 (s, 1H), 7.38 (dd, 1H), 7.29 (s, 1H), 6.67 (s, 1H), 4.69 (q, 2H), 4.54 (d, 2H), 4.08 (d, 2H), 2.22 (s, 3H), 1.76 (s, 3H)；MS (electron spray ES+)：606,608 ((M+H)+)。
Embodiment P5：Prepare table D compounds D14：(the chloro- 3- methyl-N- of 2- amino -5- (3- methyl-Thietane -3- bases)-benzamide)
Similar to embodiment P4, step 3, by Starting Materials Example P4, step 2 and embodiment P1, step 3 prepare the benzamide, obtain white solid, 92-94 DEG C of fusing point.
1H-NMR(CDCl3)：7.14 (s, 1H), 7.10 (s, 1H), 6.09 (s, 1H), 5.57 (br s, 2H), 3.90 (d, 2H), 3.03 (d, 2H), 2.14 (s, 3H), 1.83 (s, 3H)；MS (electron spray ES+)：271,273 ((M+H)+)。
Embodiment P6：Prepare table C compounds Cl3：(2,2- dimethyl-Thietane -3- bases amine)
To 2,2- dimethyl-Thietane -3- ketone is [according to W.Luettke et al., Chemische Berichte1977,110, it is prepared by 1421-31] ammonium acetate (59g, 765mmol) and sodium cyanoborohydride (7.8g are added in methanol (200ml) solution of (8.9g, 76.6mmol), 118.7mmol), and by reactant mixture it is heated to reflux 2 hours.Reactant mixture is cooled down, is purged with nitrogen.PH2 (maintaining the temperature at less than 10 DEG C) is acidified to concentrated hydrochloric acid, is concentrated under reduced pressure.Residue is poured into water, is extracted, the pH of aqueous phase is adjusted to pH11 with 30% sodium hydroxide, product is extracted with ether with ether (2x).The organic layer of merging salt water washing, dries (Na2SO4), filtering and concentration.Oily crude product (1.47g, 16%) is directly used, without being further purified.
1H-NMR(CDCl3)：3.83 (dd, 1H), 3.19 (t, 1H), 2.95 (t, 1H), 1.63 (brs, 2H), 1.50 (s, 3H), 1.42 (s, 3H).
Compound (m.p.=fusing points DEG C) listed in following table P can be prepared similar to above-mentioned step.
Table P：Compound of formula I：
Following embodiments is intended to the description and interpretation present invention, further provides preferred compound of formula I.They do not limit the present invention." Me " is methyl.
Table A：The substituent of table 1 to 44 is specified：
| OK | R91 | R92 | R93 | R35 |
| A.1.1 | Me | Cl | CF3 | H |
| A.1.2 | Me | Cl | CF3 | CH3 |
| A.1.3 | Me | Cl | CF3 | CH2CH3 |
| A.1.4 | Me | Cl | CF3 | CH2OCH3 |
| A.1.5 | Me | Cl | CF3 | CF3 |
| A.1.6 | Me | Cl | Br | H |
| A.1.7 | Me | Cl | Br | CH3 |
| A.1.8 | Me | Cl | Br | CH2CH3 |
| A.1.9 | Me | Cl | Br | CH2OCH3 |
| A.1.10 | Me | Cl | Br | CF3 |
| A.1.11 | Me | Cl | Cl | H |
| A.1.12 | Me | Cl | Cl | CH3 |
| A.1.13 | Me | Cl | Cl | CH2CH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.14 | Me | Cl | Cl | CH2OCH3 |
| A.1.15 | Me | Cl | Cl | CF3 |
| A.1.16 | Me | Cl | OCF2H | H |
| A.1.17 | Me | Cl | OCF2H | CH3 |
| A.1.18 | Me | Cl | OCF2H | CH2CH3 |
| A.1.19 | Me | Cl | OCF2H | CH2OCH3 |
| A.1.20 | Me | Cl | OCF2H | CF3 |
| A.1.21 | Me | Cl | OCH2CF3 | H |
| A.1.22 | Me | Cl | OCH2CF3 | CH3 |
| A.1.23 | Me | Cl | OCH2CF3 | CH2CH3 |
| A.1.24 | Me | Cl | OCH2CF3 | CH2OCH3 |
| A.1.25 | Me | Cl | OCH2CF3 | CF3 |
| A.1.26 | Me | Cl | OCF3 | H |
| A.1.27 | Me | Cl | OCF3 | CH3 |
| A.1.28 | Me | Cl | OCF3 | CH2CH3 |
| A.1.29 | Me | Cl | OCF3 | CH2OCH3 |
| A.1.30 | Me | Cl | OCF3 | CF3 |
| A.1.31 | Me | Br | CF3 | H |
| A.1.32 | Me | Br | CF3 | CH3 |
| A.1.33 | Me | Br | CF3 | CH2CH3 |
| A.1.34 | Me | Br | CF3 | CH2OCH3 |
| A.1.35 | Me | Br | CF3 | CF3 |
| A.1.36 | Me | Br | Br | H |
| A.1.37 | Me | Br | Br | CH3 |
| A.1.38 | Me | Br | Br | CH2CH3 |
| A.1.39 | Me | Br | Br | CH2OCH3 |
| A.1.40 | Me | Br | Br | CF3 |
| A.1.41 | Me | Br | Cl | H |
| A.1.42 | Me | Br | Cl | CH3 |
| A.1.43 | Me | Br | Cl | CH2CH3 |
| A.1.44 | Me | Br | Cl | CH2OCH3 |
| A.1.45 | Me | Br | Cl | CF3 |
| A.1.46 | Me | Br | OCF2H | H |
| A.1.47 | Me | Br | OCF2H | CH3 |
| A.1.48 | Me | Br | OCF2H | CH2CH3 |
| A.1.49 | Me | Br | OCF2H | CH2OCH3 |
| A.1.50 | Me | Br | OCF2H | CF3 |
| A.1.51 | Me | Br | OCH2CF3 | H |
| A.1.52 | Me | Br | OCH2CF3 | CH3 |
| A.1.53 | Me | Br | OCH2CF3 | CH2CH3 |
| A.1.54 | Me | Br | OCH2CF3 | CH2OCH3 |
| A.1.55 | Me | Br | OCH2CF3 | CF3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.56 | Me | Br | OCF3 | H |
| A.1.57 | Me | Br | OCF3 | CH3 |
| A.1.58 | Me | Br | OCF3 | CH2CH3 |
| A.1.59 | Me | Br | OCF3 | CH2OCH3 |
| A.1.60 | Me | Br | OCF3 | CF3 |
| A.1.61 | Me | F | CF3 | H |
| A.1.62 | Me | F | CF3 | CH3 |
| A.1.63 | Me | F | CF3 | CH2CH3 |
| A.1.64 | Me | F | CF3 | CH2OCH3 |
| A.1.65 | Me | F | CF3 | CF3 |
| A.1.66 | Me | F | Br | H |
| A.1.67 | Me | F | Br | CH3 |
| A.1.68 | Me | F | Br | CH2CH3 |
| A.1.69 | Me | F | Br | CH2OCH3 |
| A.1.70 | Me | F | Br | CF3 |
| A.1.71 | Me | F | Cl | H |
| A.1.72 | Me | F | Cl | CH3 |
| A.1.73 | Me | F | Cl | CH2CH3 |
| A.1.74 | Me | F | Cl | CH2OCH3 |
| A.1.75 | Me | F | Cl | CF3 |
| A.1.76 | Me | F | OCF2H | H |
| A.1.77 | Me | F | OCF2H | CH3 |
| A.1.78 | Me | F | OCF2H | CH2CH3 |
| A.1.79 | Me | F | OCF2H | CH2OCH3 |
| A.1.80 | Me | F | OCF2H | CF3 |
| A.1.81 | Me | F | OCH2CF3 | H |
| A.1.82 | Me | F | OCH2CF3 | CH3 |
| A.1.83 | Me | F | OCH2CF3 | CH2CH3 |
| A.1.84 | Me | F | OCH2CF3 | CH2OCH3 |
| A.1.85 | Me | F | OCH2CF3 | CF3 |
| A.1.86 | Me | F | OCF3 | H |
| A.1.87 | Me | F | OCF3 | CH3 |
| A.1.88 | Me | F | OCF3 | CH2CH3 |
| A.1.89 | Me | F | OCF3 | CH2OCH3 |
| A.1.90 | Me | F | OCF3 | CF3 |
| A.1.91 | Me | CN | CF3 | H |
| A.1.92 | Me | CN | CF3 | CH3 |
| A.1.93 | Me | CN | CF3 | CH2CH3 |
| A.1.94 | Me | CN | CF3 | CH2OCH3 |
| A.1.95 | Me | CN | CF3 | CF3 |
| A.1.96 | Me | CN | Br | H |
| A.1.97 | Me | CN | Br | CH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.98 | Me | CN | Br | CH2CH3 |
| A.1.99 | Me | CN | Br | CH2OCH3 |
| A.1.100 | Me | CN | Br | CF3 |
| A.1.101 | Me | CN | Cl | H |
| A.1.102 | Me | CN | Cl | CH3 |
| A.1.103 | Me | CN | Cl | CH2CH3 |
| A.1.104 | Me | CN | Cl | CH2OCH3 |
| A.1.105 | Me | CN | Cl | CF3 |
| A.1.106 | Me | CN | OCF2H | H |
| A.1.107 | Me | CN | OCF2H | CH3 |
| A.1.108 | Me | CN | OCF2H | CH2CH3 |
| A.1.109 | Me | CN | OCF2H | CH2OCH3 |
| A.1.110 | Me | CN | OCF2H | CF3 |
| A.1.111 | Me | CN | OCH2CF3 | H |
| A.1.112 | Me | CN | OCH2CF3 | CH3 |
| A.1.113 | Me | CN | OCH2CF3 | CH2CH3 |
| A.1.114 | Me | CN | OCH2CF3 | CH2OCH3 |
| A.1.115 | Me | CN | OCH2CF3 | CF3 |
| A.1.116 | Me | CN | OCF3 | H |
| A.1.117 | Me | CN | OCF3 | CH3 |
| A.1.118 | Me | CN | OCF3 | CH2CH3 |
| A.1.119 | Me | CN | OCF3 | CH2OCH3 |
| A.1.120 | Me | CN | OCF3 | CF3 |
| A.1.121 | Cl | Cl | CF3 | H |
| A.1.122 | Cl | Cl | CF3 | CH3 |
| A.1.123 | Cl | Cl | CF3 | CH2CH3 |
| A.1.124 | Cl | Cl | CF3 | CH2OCH3 |
| A.1.125 | Cl | Cl | CF3 | CF3 |
| A.1.126 | Cl | Cl | Br | H |
| A.1.127 | Cl | Cl | Br | CH3 |
| A.1.128 | Cl | Cl | Br | CH2CH3 |
| A.1.129 | Cl | Cl | Br | CH2OCH3 |
| A.1.130 | Cl | Cl | Br | CF3 |
| A.1.131 | Cl | Cl | Cl | H |
| A.1.132 | Cl | Cl | Cl | CH3 |
| A.1.133 | Cl | Cl | Cl | CH2CH3 |
| A.1.134 | Cl | Cl | Cl | CH2OCH3 |
| A.1.135 | Cl | Cl | Cl | CF3 |
| A.1.136 | Cl | Cl | OCF2H | H |
| A.1.137 | Cl | Cl | OCF2H | CH3 |
| A.1.138 | Cl | Cl | OCF2H | CH2CH3 |
| A.1.139 | Cl | Cl | OCF2H | CH2OCH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.140 | Cl | Cl | OCF2H | CF3 |
| A.1.141 | Cl | Cl | OCH2CF3 | H |
| A.1.142 | Cl | Cl | OCH2CF3 | CH3 |
| A.1.143 | Cl | Cl | OCH2CF3 | CH2CH3 |
| A.1.144 | Cl | Cl | OCH2CF3 | CH2OCH3 |
| A.1.145 | Cl | Cl | OCH2CF3 | CF3 |
| A.1.146 | Cl | Cl | OCF3 | H |
| A.1.147 | Cl | Cl | OCF3 | CH3 |
| A.1.148 | Cl | Cl | OCF3 | CH2CH3 |
| A.1.149 | Cl | Cl | OCF3 | CH2OCH3 |
| A.1.150 | Cl | Cl | OCF3 | CF3 |
| A.1.151 | Cl | Br | CF3 | H |
| A.1.152 | Cl | Br | CF3 | CH3 |
| A.1.153 | Cl | Br | CF3 | CH2CH3 |
| A.1.154 | Cl | Br | CF3 | CH2OCH3 |
| A.1.155 | Cl | Br | CF3 | CF3 |
| A.1.156 | Cl | Br | Br | H |
| A.1.157 | Cl | Br | Br | CH3 |
| A.1.158 | Cl | Br | Br | CH2CH3 |
| A.1.159 | Cl | Br | Br | CH2OCH3 |
| A.1.160 | Cl | Br | Br | CF3 |
| A.1.161 | Cl | Br | C1 | H |
| A.1.162 | Cl | Br | C1 | CH3 |
| A.1.163 | Cl | Br | C1 | CH2CH3 |
| A.1.164 | Cl | Br | C1 | CH2OCH3 |
| A.1.165 | Cl | Br | C1 | CF3 |
| A.1.166 | Cl | Br | OCF2H | H |
| A.1.167 | Cl | Br | OCF2H | CH3 |
| A.1.168 | Cl | Br | OCF2H | CH2CH3 |
| A.1.169 | Cl | Br | OCF2H | CH2OCH3 |
| A.1.170 | Cl | Br | OCF2H | CF3 |
| A.1.171 | Cl | Br | OCH2CF3 | H |
| A.1.172 | Cl | Br | OCH2CF3 | CH3 |
| A.1.173 | Cl | Br | OCH2CF3 | CH2CH3 |
| A.1.174 | Cl | Br | OCH2CF3 | CH2OCH3 |
| A.1.175 | Cl | Br | OCH2CF3 | CF3 |
| A.1.176 | Cl | Br | OCF3 | H |
| A.1.177 | Cl | Br | OCF3 | CH3 |
| A.1.178 | Cl | Br | OCF3 | CH2CH3 |
| A.1.179 | Cl | Br | OCF3 | CH2OCH3 |
| A.1.180 | Cl | Br | OCF3 | CF3 |
| A.1.181 | Cl | F | CF3 | H |
| OK | R91 | R92 | R93 | R35 |
| A.1.182 | Cl | F | CF3 | CH3 |
| A.1.183 | Cl | F | CF3 | CH2CH3 |
| A.1.184 | Cl | F | CF3 | CH2OCH3 |
| A.1.185 | Cl | F | CF3 | CF3 |
| A.1.186 | Cl | F | Br | H |
| A.1.187 | Cl | F | Br | CH3 |
| A.1.188 | Cl | F | Br | CH2CH3 |
| A.1.189 | Cl | F | Br | CH2OCH3 |
| A.1.190 | Cl | F | Br | CF3 |
| A.1.191 | Cl | F | Cl | H |
| A.1.192 | Cl | F | Cl | CH3 |
| A.1.193 | Cl | F | Cl | CH2CH3 |
| A.1.194 | Cl | F | Cl | CH2OCH3 |
| A.1.195 | Cl | F | Cl | CF3 |
| A.1.196 | Cl | F | OCF2H | H |
| A.1.197 | Cl | F | OCF2H | CH3 |
| A.1.198 | Cl | F | OCF2H | CH2CH3 |
| A.1.199 | Cl | F | OCF2H | CH2OCH3 |
| A.1.200 | Cl | F | OCF2H | CF3 |
| A.1.201 | Cl | F | OCH2CF3 | H |
| A.1.202 | Cl | F | OCH2CF3 | CH3 |
| A.1.203 | Cl | F | OCH2CF3 | CH2CH3 |
| A.1.204 | Cl | F | OCH2CF3 | CH2OCH3 |
| A.1.205 | Cl | F | OCH2CF3 | CF3 |
| A.1.206 | Cl | F | OCF3 | H |
| A.1.207 | Cl | F | OCF3 | CH3 |
| A.1.208 | Cl | F | OCF3 | CH2CH3 |
| A.1.209 | Cl | F | OCF3 | CH2OCH3 |
| A.1.210 | Cl | F | OCF3 | CF3 |
| A.1.211 | Cl | CN | CF2 | H |
| A.1.212 | Cl | CN | CF3 | CH3 |
| A.1.213 | Cl | CN | CF3 | CH2CH3 |
| A.1.214 | Cl | CN | CF3 | CH2OCH3 |
| A.1.215 | Cl | CN | CF3 | CF3 |
| A.1.216 | Cl | CN | Br | H |
| A.1.217 | Cl | CN | Br | CH3 |
| A.1.218 | Cl | CN | Br | CH2CH3 |
| A.1.219 | Cl | CN | Br | CH2OCH3 |
| A.1.220 | Cl | CN | Br | CF3 |
| A.1.221 | Cl | CN | Cl | H |
| A.1.222 | Cl | CN | Cl | CH3 |
| A.1.223 | Cl | CN | Cl | CH2CH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.224 | Cl | CN | Cl | CH2OCH3 |
| A.1.225 | Cl | CN | Cl | CF3 |
| A.1.226 | Cl | CN | OCF2H | H |
| A.1.227 | Cl | CN | OCF2H | CH3 |
| A.1.228 | Cl | CN | OCF2H | CH2CH3 |
| A.1.229 | Cl | CN | OCF2H | CH2OCH3 |
| A.1.230 | Cl | CN | OCF2H | CF3 |
| A.1.231 | Cl | CN | OCH2CF3 | H |
| A.1.232 | Cl | CN | OCH2CF3 | CH3 |
| A.1.233 | Cl | CN | OCH2CF3 | CH2CH3 |
| A.1.234 | Cl | CN | OCH2CF3 | CH2OCH3 |
| A.1.235 | Cl | CN | OCH2CF3 | CF3 |
| A.1.236 | Cl | CN | OCF3 | H |
| A.1.237 | Cl | CN | OCF3 | CH3 |
| A.1.238 | Cl | CN | OCF3 | CH2CH3 |
| A.1.239 | Cl | CN | OCF3 | CH2OCH3 |
| A.1.240 | Cl | CN | OCF3 | CF3 |
| A.1.241 | Br | C1 | CF3 | H |
| A.1.242 | Br | C1 | CF3 | CH3 |
| A.1.243 | Br | C1 | CF3 | CH2CH3 |
| A.1.244 | Br | C1 | CF3 | CH2OCH3 |
| A.1.245 | Br | C1 | CF3 | CF3 |
| A.1.246 | Br | C1 | Br | H |
| A.1.247 | Br | C1 | Br | CH3 |
| A.1.248 | Br | C1 | Br | CH2CH3 |
| A.1.249 | Br | C1 | Br | CH2OCH3 |
| A.1.250 | Br | C1 | Br | CF3 |
| A.1.251 | Br | C1 | Cl | H |
| A.1.252 | Br | C1 | Cl | CH3 |
| A.1.253 | Br | C1 | Cl | CH2CH3 |
| A.1.254 | Br | C1 | Cl | CH2OCH3 |
| A.1.255 | Br | C1 | Cl | CF3 |
| A.1.256 | Br | C1 | OCF2H | H |
| A.1.257 | Br | C1 | OCF2H | CH3 |
| A.1.258 | Br | C1 | OCF2H | CH2CH3 |
| A.1.259 | Br | C1 | OCF2H | CH2OCH3 |
| A.1.260 | Br | C1 | OCF2H | CF3 |
| A.1.261 | Br | C1 | OCH2CF3 | H |
| A.1.262 | Br | C1 | OCH2CF3 | CH3 |
| A.1.263 | Br | C1 | OCH2CF3 | CH2CH3 |
| A.1.264 | Br | C1 | OCH2CF3 | CH2OCH3 |
| A.1.265 | Br | C1 | OCH2CF3 | CF3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.266 | Br | Cl | OCF3 | H |
| A.1.267 | Br | Cl | OCF3 | CH3 |
| A.1.268 | Br | Cl | OCF3 | CH2CH3 |
| A.1.269 | Br | Cl | OCF3 | CH2OCH3 |
| A.1.270 | Br | Cl | OCF3 | CF3 |
| A.1.271 | Br | Br | CF3 | H |
| A.1.272 | Br | Br | CF3 | CH3 |
| A.1.273 | Br | Br | CF3 | CH2CH3 |
| A.1.274 | Br | Br | CF3 | CH2OCH3 |
| A.1.275 | Br | Br | CF3 | CF3 |
| A.1.276 | Br | Br | Br | H |
| A.1.277 | Br | Br | Br | CH3 |
| A.1.278 | Br | Br | Br | CH2CH3 |
| A.1.279 | Br | Br | Br | CH2OCH3 |
| A.1.280 | Br | Br | Br | CF3 |
| A.1.281 | Br | Br | Cl | H |
| A.1.282 | Br | Br | Cl | CH3 |
| A.1.283 | Br | Br | Cl | CH2CH3 |
| A.1.284 | Br | Br | Cl | CH2OCH3 |
| A.1.285 | Br | Br | Cl | CF3 |
| A.1.286 | Br | Br | OCF2H | H |
| A.1.287 | Br | Br | OCF2H | CH3 |
| A.1.288 | Br | Br | OCF2H | CH2CH3 |
| A.1.289 | Br | Br | OCF2H | CH2OCH3 |
| A.1.290 | Br | Br | OCF2H | CF3 |
| A.1.291 | Br | Br | OCH2CF3 | H |
| A.1.292 | Br | Br | OCH2CF3 | CH3 |
| A.1.293 | Br | Br | OCH2CF3 | CH2CH3 |
| A.1.294 | Br | Br | OCH2CF3 | CH2OCH3 |
| A.1.295 | Br | Br | OCH2CF3 | CF3 |
| A.1.296 | Br | Br | OCF3 | H |
| A.1.297 | Br | Br | OCF3 | CH3 |
| A.1.298 | Br | Br | OCF3 | CH2CH3 |
| A.1.299 | Br | Br | OCF3 | CH2OCH3 |
| A.1.300 | Br | Br | OCF3 | CF3 |
| A.1.301 | Br | F | CF3 | H |
| A.1.302 | Br | F | CF3 | CH3 |
| A.1.303 | Br | F | CF3 | CH2CH3 |
| A.1.304 | Br | F | CF3 | CH2OCH3 |
| A.1.305 | Br | F | CF3 | CF3 |
| A.1.306 | Br | F | Br | H |
| A.1.307 | Br | F | Br | CH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.308 | Br | F | Br | CH2CH3 |
| A.1.309 | Br | F | Br | CH2OCH3 |
| A.1.310 | Br | F | Br | CF3 |
| A.1.311 | Br | F | Cl | H |
| A.1.312 | Br | F | Cl | CH3 |
| A.1.313 | Br | F | Cl | CH2CH3 |
| A.1.314 | Br | F | Cl | CH2OCH3 |
| A.1.315 | Br | F | Cl | CF3 |
| A.1.316 | Br | F | OCF2H | H |
| A.1.317 | Br | F | OCF2H | CH3 |
| A.1.318 | Br | F | OCF2H | CH2CH3 |
| A.1.319 | Br | F | OCF2H | CH2OCH3 |
| A.1.320 | Br | F | OCF2H | CF3 |
| A.1.321 | Br | F | OCH2CF3 | H |
| A.1.322 | Br | F | OCH2CF3 | CH3 |
| A.1.323 | Br | F | OCH2CF3 | CH2CH3 |
| A.1.324 | Br | F | OCH2CF3 | CH2OCH3 |
| A.1.325 | Br | F | OCH2CF3 | CF3 |
| A.1.326 | Br | F | OCF3 | H |
| A.1.327 | Br | F | OCF3 | CH3 |
| A.1.328 | Br | F | OCF3 | CH2CH3 |
| A.1.329 | Br | F | OCF3 | CH2OCH3 |
| A.1.330 | Br | F | OCF3 | CF3 |
| A.1.331 | Br | CN | CF3 | H |
| A.1.332 | Br | CN | CF3 | CH3 |
| A.1.333 | Br | CN | CF3 | CH2CH3 |
| A.1.334 | Br | CN | CF3 | CH2OCH3 |
| A.1.335 | Br | CN | CF3 | CF3 |
| A.1.336 | Br | CN | Br | H |
| A.1.337 | Br | CN | Br | CH3 |
| A.1.338 | Br | CN | Br | CH2CH3 |
| A.1.339 | Br | CN | Br | CH2OCH3 |
| A.1.340 | Br | CN | Br | CF3 |
| A.1.341 | Br | CN | Cl | H |
| A.1.342 | Br | CN | Cl | CH3 |
| A.1.343 | Br | CN | Cl | CH2CH3 |
| A.1.344 | Br | CN | Cl | CH2OCH3 |
| A.1.345 | Br | CN | Cl | CF3 |
| A.1.346 | Br | CN | OCF2H | H |
| A.1.347 | Br | CN | OCF2H | CH3 |
| A.1.348 | Br | CN | OCF2H | CH2CH3 |
| A.1.349 | Br | CN | OCF2H | CH2OCH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.350 | Br | CN | OCF2H | CF3 |
| A.1.351 | Br | CN | OCH2CF3 | H |
| A.1.352 | Br | CN | OCH2CF3 | CH3 |
| A.1.353 | Br | CN | OCH2CF3 | CH2CH3 |
| A.1.354 | Br | CN | OCH2CF3 | CH2OCH3 |
| A.1.355 | Br | CN | OCH2CF3 | CF3 |
| A.1.356 | Br | CN | OCF3 | H |
| A.1.357 | Br | CN | OCF3 | CH3 |
| A.1.358 | Br | CN | OCF3 | CH2CH3 |
| A.1.359 | Br | CN | OCF3 | CH2OCH3 |
| A.1.360 | Br | CN | OCF3 | CF3 |
| A.1.361 | Me | H | CF3 | H |
| A.1.362 | Me | H | CF3 | CH3 |
| A.1.363 | Me | H | CF3 | CH2CH3 |
| A.1.364 | Me | H | CF3 | CH2OCH3 |
| A.1.365 | Me | H | CF3 | CF3 |
| A.1.366 | Me | H | Br | H |
| A.1.367 | Me | H | Br | CH3 |
| A.1.368 | Me | H | Br | CH2CH3 |
| A.1.369 | Me | H | Br | CH2OCH3 |
| A.1.370 | Me | H | Br | CF3 |
| A.1.371 | Me | H | C1 | H |
| A.1.372 | Me | H | C1 | CH3 |
| A.1.373 | Me | H | C1 | CH2CH3 |
| A.1.374 | Me | H | C1 | CH2OCH3 |
| A.1.375 | Me | H | C1 | CF3 |
| A.1.376 | Me | H | OCF2H | H |
| A.1.377 | Me | H | OCF2H | CH3 |
| A.1.378 | Me | H | OCF2H | CH2CH3 |
| A.1.379 | Me | H | OCF2H | CH2OCH3 |
| A.1.380 | Me | H | OCF2H | CF3 |
| A.1.381 | Me | H | OCH2CF3 | H |
| A.1.382 | Me | H | OCH2CF3 | CH3 |
| A.1.383 | Me | H | OCH2CF3 | CH2CH3 |
| A.1.384 | Me | H | OCH2CF3 | CH2OCH3 |
| A.1.385 | Me | H | OCH2CF3 | CF3 |
| A.1.386 | Me | H | OCF3 | H |
| A.1.387 | Me | H | OCF3 | CH3 |
| A.1.388 | Me | H | OCF3 | CH2CH3 |
| A.1.389 | Me | H | OCF3 | CH2OCH3 |
| A.1.390 | Me | H | OCF3 | CF3 |
| A.1.391 | Cl | H | CF3 | H |
| OK | R91 | R92 | R93 | R35 |
| A.1.392 | Cl | H | CF3 | CH3 |
| A.1.393 | Cl | H | CF3 | CH2CH3 |
| A.1.394 | Cl | H | CF3 | CH2OCH3 |
| A.1.395 | Cl | H | CF3 | CF3 |
| A.1.396 | Cl | H | Br | H |
| A.1.397 | Cl | H | Br | CH3 |
| A.1.398 | Cl | H | Br | CH2CH3 |
| A.1.399 | Cl | H | Br | CH2OCH3 |
| A.1.400 | Cl | H | Br | CF3 |
| A.1.401 | Cl | H | C1 | H |
| A.1.402 | Cl | H | C1 | CH3 |
| A.1.403 | Cl | H | C1 | CH2CH3 |
| A.1.404 | Cl | H | C1 | CH2OCH3 |
| A.1.405 | Cl | H | C1 | CF3 |
| A.1.406 | Cl | H | OCF2H | H |
| A.1.407 | Cl | H | OCF2H | CH3 |
| A.1.408 | Cl | H | OCF2H | CH2CH3 |
| A.1.409 | Cl | H | OCF2H | CH2OCH3 |
| A.1.410 | Cl | H | OCF2H | CF3 |
| A.1.411 | Cl | H | OCH2CF3 | H |
| A.1.412 | Cl | H | OCH2CF3 | CH3 |
| A.1.413 | Cl | H | OCH2CF3 | CH2CH3 |
| A.1.414 | Cl | H | OCH2CF3 | CH2OCH3 |
| A.1.415 | Cl | H | OCH2CF3 | CF3 |
| A.1.416 | Cl | H | OCF3 | H |
| A.1.417 | Cl | H | OCF3 | CH3 |
| A.1.418 | Cl | H | OCF3 | CH2CH3 |
| A.1.419 | Cl | H | OCF3 | CH2OCH3 |
| A.1.420 | Cl | H | OCF3 | CF3 |
| A.1.421 | Me | Cl | CHF2 | H |
| A.1.422 | Me | Cl | CHF2 | CH3 |
| A.1.423 | Me | Cl | CHF2 | CH2CH3 |
| A.1.424 | Me | Cl | CHF2 | CH2OCH3 |
| A.1.425 | Me | Cl | CHF2 | CF3 |
| A.1.426 | Me | Br | CHF2 | H |
| A.1.427 | Me | Br | CHF2 | CH3 |
| A.1.428 | Me | Br | CHF2 | CH2CH3 |
| A.1.429 | Me | Br | CHF2 | CH2OCH3 |
| A.1.430 | Me | Br | CHF2 | CF3 |
| A.1.431 | Me | CN | CHF2 | H |
| A.1.432 | Me | CN | CHF2 | CH3 |
| A.1.433 | Me | CN | CHF2 | CH2CH3 |
| OK | R91 | R92 | R93 | R35 |
| A.1.434 | Me | CN | CHF2 | CH2OCH3 |
| A.1.435 | Me | CN | CHF2 | CF3 |
| A.1.436 | Cl | Cl | CHF2 | H |
| A.1.437 | Cl | Cl | CHF2 | CH3 |
| A.1.438 | Cl | Cl | CHF2 | CH2CH3 |
| A.1.439 | Cl | Cl | CHF2 | CH2OCH3 |
| A.1.440 | Cl | Cl | CHF2 | CF3 |
| A.1.441 | Cl | Br | CHF2 | H |
| A.1.442 | Cl | Br | CHF2 | CH3 |
| A.1.443 | Cl | Br | CHF2 | CH2CH3 |
| A.1.444 | Cl | Br | CHF2 | CH2OCH3 |
| A.1.445 | Cl | Br | CHF2 | CF3 |
| A.1.446 | Cl | CN | CHF2 | H |
| A.1.447 | Cl | CN | CHF2 | CH3 |
| A.1.448 | Cl | CN | CHF2 | CH2CH3 |
| A.1.449 | Cl | CN | CHF2 | CH2OCH3 |
| A.1.450 | Cl | CN | CHF2 | CF3 |
| A.1.451 | Br | Cl | CHF2 | H |
| A.1.452 | Br | Cl | CHF2 | CH3 |
| A.1.453 | Br | Cl | CHF2 | CH2CH3 |
| A.1.454 | Br | Cl | CHF2 | CH2OCH3 |
| A.1.455 | Br | Cl | CHF2 | CF3 |
| A.1.456 | Br | Br | CHF2 | H |
| A.1.457 | Br | Br | CHF2 | CH3 |
| A.1.458 | Br | Br | CHF2 | CH2CH3 |
| A.1.459 | Br | Br | CHF2 | CH2OCH3 |
| A.1.460 | Br | Br | CHF2 | CF3 |
| A.1.461 | Br | CN | CHF2 | H |
| A.1.462 | Br | CN | CHF2 | CH3 |
| A.1.463 | Br | CN | CHF2 | CH2CH3 |
| A.1.464 | Br | CN | CHF2 | CH2OCH3 |
| A.1.465 | Br | CN | CHF2 | CF3 |
Table 1：This table discloses 465 following formula: compound T1.1.1 to T1.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
For example, particular compound T1.1.23 is formula T1 compounds, wherein the variable R91、R92、R93And R35Each with Table A A.1.23 given in the concrete meaning that goes out.According to the identical system, 359 particular compounds of others disclosed in table 1 and all particular compounds disclosed in table 2 to table 44 are similarly specified.
Table 2：This table discloses 465 following formula: compound T2.1.1 to T2.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 3：This table discloses 465 following formula: compound T3.1.1 to T3.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 4：This table discloses 465 following formula: compound T4.1.1 to T4.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 5：This table discloses 465 following formula: compound T5.1.1 to T5.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 6：This table discloses 465 following formula: compound T6.1.1 to T6.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 7：This table discloses 465 following formula: compound T7.1.1 to T7.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 8：This table discloses 465 following formula: compound T8.1.1 to T8.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 9：This table discloses 465 following formula: compound T9.1.1 to T9.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 10：This table discloses 465 following formula: compound T10.1.1 to T10.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 11：This table discloses 465 following formula: compound T11.1.1 to T11.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 12：This table discloses 465 following formula: compound T12.1.1 to T12.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 13：This table discloses 465 following formula: compound T13.1.1 to T13.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 14：This table discloses 465 following formula: compound T14.1.1 to T14.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 15：This table discloses 465 following formula: compound T15.1.1 to T15.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 16：This table discloses 465 following formula: compound T16.1.1 to T16.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 17：This table discloses 465 following formula: compound T17.1.1 to T17.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 18：This table discloses 465 following formula: compound T18.1.1T18.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 19：This table discloses 465 following formula: compound T19.1.1 to T19.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 20：This table discloses 465 following formula: compound T20.1.1 to T20.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 21：This table discloses 465 following formula: compound T21.1.1 to T21.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 22：This table discloses 465 following formula: compound T22.1.1 to T22.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 23：This table discloses 465 following formula: compound T23.1.1 to T23.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 24：This table discloses 465 following formula: compound T24.1.1 to T24.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 25：This table discloses 465 following formula: compound T25.1.1 to T25.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 26：This table discloses 465 following formula: compound T26.1.1 to T26.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 27：This table discloses 465 following formula: compound T27.1.1 to T27.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 28：This table discloses 465 following formula: compound T28.1.1 to T28.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 29：This table discloses 465 following formula: compound T29.1.1 to T29.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 30：This table discloses 465 following formula: compound T30.1.1 to T30.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 31：This table discloses 465 following formula: compound T31.1.1 to T31.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 32：This table discloses 465 following formula: compound T32.1.1 to T32.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 33：This table discloses 465 following formula: compound T33.1.1 to T33.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 34：This table discloses 465 following formula: compound T34.1.1 to T34.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 35：This table discloses 465 following formula: compound T35.1.1 to T35.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 36：This table discloses 465 following formula: compound T36.1.1 to T36.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 37：This table discloses 465 following formula: compound T37.1.1 to T37.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 38：This table discloses 465 following formula: compound T38.1.1 to T38.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 39：This table discloses 465 following formula: compound T39.1.1 to T39.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 40：This table discloses 465 following formula: compound T40.1.1 to T40.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 41：This table discloses 465 following formula: compound T41.1.1 to T41.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 42：This table discloses 465 following formula: compound T42.1.1 to T42.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 43：This table discloses 465 following formula: compound T43.1.1 to T43.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Table 44：This table discloses 465 following formula: compound T44.1.1 to T44.1.465
Wherein, for each of this 465 particular compounds, the variable R91、R92、R93And R35Each there are appropriate 465 rows selected from Table A A.1.1 to the concrete meaning gone out given in corresponding line A.1.465.
Formulation Example(%=percentage by weights)
Embodiment F1：Emulsifiable concentrate a) b) c)
Active component 25% 40% 50%
Calcium dodecyl benzene sulfonate 5% 8% 6%
Castor oil polyglycol ether (36 moles of EO) 5%--
Tributyl phenoxy group polyglycol ether (30 moles of EO) -12% 4%
Cyclohexanone -15% 20%
Xylene mixture 65% 25% 20%
Thus any emulsion for wishing concentration can be made by concentrate by being diluted with water.
Embodiment F2：Solution a) b) c) d)
Active component 80% 10% 5% 95%
Glycol monoethyl ether 20%---
Polyethylene glycol MW 400-70%--
NMP -20%--
Epoxidised coconut oil--1% 5%
Petroleum ether (boiling range：160-190 °)--94% -
The solution is adapted to use with droplet form.
Embodiment F3：Granule a) b) c) d)
Active component 5% 10% 8% 21%
Kaolin 94% -79% 54%
Aerosil 200 1% -13% 7%
Attapulgite -90% -18%
Active component is dissolved in dichloromethane, solution is sprayed onto on carrier, subsequent vacuum evaporating solvent.
Embodiment F4：Pulvis a) b)
Active component 2% 5%
Aerosil 200 1% 5%
Talcum 97%-
Kaolin -90%
It is by the way that carrier and active component are mixed into acquisition closely i.e. with pulvis.
Embodiment F5：Wettable powder a) b) c)
Active component 25% 50% 75%
Sodium lignin sulfonate 5% 5%-
NaLS 3% -5%
Diisobutyl sodium naphthalene sulfonate -6% 10%
Octylphenoxy polyglycol ether
(7-8 moles of EO) -2% -
Aerosil 200 5% 10% 10%
Kaolin 62% 27%-
By active component and additive agent mixture, mixture is fully ground in suitable mill.Wettable powder is thus produced, is diluted with water and produces any suspension for wishing concentration.
Embodiment F6：Extrude granule
Active component 10%
Sodium lignin sulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 87%
Grind, soaked with water by active component and additive agent mixture, and by mixture, extrude and dry in the air stream.
Embodiment F7：Coated particle agent
Active component 3%
Polyethylene glycol (MW200) 3%
Kaolin 94%
In a mixer, by the active component even spread of fine lapping to the kaolin soaked with polyethylene glycol.The dustless coated particle agent thus produced.
Embodiment F8：Concentrate colloidal suspending agent
Active component 40%
Ethylene glycol 10%
Nonylphenoxy polyglycol ether (15 moles of E0) 6%
Sodium lignin sulfonate 10%
Carboxymethyl cellulose 1%
37% formalin 0.2%
Silicone oil (75% aqueous emulsion) 0.8%
Water 32%
The active component of fine lapping is mixed closely with additive.Any suspension for wishing concentration can be prepared by the way that so obtained concentration colloidal suspending agent is diluted with water.
By adding other desinsections or acaricidal activity composition can significantly widen the activity of the present composition and adapt it to main environment.The active component suitably added herein is the representative of the active component of for example following classification：Organic phosphorus compound, nitrophenol derivative, Thiourea; juvenile hormone, formamidine, benzophenone derivates; ureas, azole derivatives, carbamates; pyrethroid; chlorinated hydrocarbon, acyl group ureas, pyridylmethylene amino derivative; macrolides, anabasine and sporeine preparation.
The following mixture of compound of formula I and other active components is preferred (abbreviation " TX " expression " compound in the compound group that a kind of table T1 selected from the present invention is specifically described into T44 ")：
Auxiliary agent+TX selected from petroleum-type oily (alias) (628),
It is selected from the group the acaricide of material：1,1- bis- (4- chlorphenyls)-cellosolvo (IUPAC titles) (910)+TX,2,4- dichlorophenyls benzene sulfonate (IUPAC/ chemical abstracts name) (1059)+TX,The fluoro- N- methyl-N-1- NADs of 2- (IUPAC titles) (1295)+TX,4- chlorophenyl phenyl sulfones (IUPAC titles) (981)+TX,AVM (1)+TX,Acequinocyl (3)+TX,Acetyl worm nitrile [CCN]+TX,Acrinathrin (9)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,O- cypermethrins (202)+TX,Amidithion (870)+TX,Sulfanilamide (SN) mite ester [CCN]+TX,amidothioate(872)+TX,Citram (875)+TX,Citram binoxalate (875)+TX,Amitraz (24)+TX,Aramite (881)+TX,Arsenic trioxide (882)+TX,AVI382 (compound code)+TX,AZ60541 (compound code)+TX,Azinphos ethyl (44)+TX,Azinphos-methyl (45)+TX,Azobenzene (IUPAC titles) (888)+TX,Azacyclotin (46)+TX,Alamos (889)+TX,Benomyl (62)+TX,Cao Evil phosphorus (alias) [CCN]+TX,Citrazon (71)+TX,Ergol (IUPAC titles) [CCN]+TX,Bifenazate (74)+TX,Bifenthrin (76)+TX,Binapacryl (907)+TX,Brofenxalerate (alias)+TX,Bromocyclne (918)+TX,Bromophos (920)+TX,Rilariol (921)+TX,Fenisobromolate (94)+TX,Buprofezin (99)+TX,Butocarboxim (103)+TX,Butanone sulfone prestige (104)+TX,Butyl pyridaben (alias)+TX,Lime sulfur (IUPAC titles) (111)+TX,Toxaphene (941)+TX,Sok (943)+TX,Carbaryl (115)+TX,Carbofuran (118)+TX,Carbophenothion (947)+TX,CGA50 ' 439 (research code) (125)+TX,Chinomethionat (126)+TX,Neotran (959)+TX,Spanon (964)+TX,Chlordimeform-hydrochloride (964)+TX,Chlorfenapyr (130)+TX,Qikron (968)+TX,Chlorfenizon (970)+TX,Chlorfensulphide (971)+TX,Chlorfenviphos (131)+TX,Chlorobenzilate (975)+TX,Yi Tuoming (977)+TX,Chloromethiuron (978)+TX,Acaralate (983)+TX,Chlopyrifos (145)+TX,Chlorpyrifos-methyl (146)+TX,Actellic (994)+TX,Cinerin (696)+TX,Cinerin I (696)+TX,II cinerin II (696)+TX,Clofentezine (158)+TX,Closantel (alias) [CCN]+TX,Resistox (174)+TX,Crotonocyl toluidines (alias) [CCN]+TX,Crotoxyphos (1010)+TX,Cufraneb (1013)+TX,Cyanthoate (1020)+TX,Cyflumetofen (cyflumetofen) (CAS registration numbers：400882-07-7)+TX,Lambda-cyhalothrin (196)+TX,Plictran (199)+TX,Cypermethrin (201)+TX,DCPM(1032)+TX,DDT(219)+TX,Demephion (1037)+TX,Demephion-O (1037)+TX,Demephion-S (1037)+TX,Demeton (1038)+TX,Demeton-methyl (224)+TX,Demeton-O (1038)+TX,Demeton-methyl -0 (224)+TX,Demeton-S (1038)+TX,Demeton-methyl-S (224)+TX,Metilomerkaptofosoksid (1039)+TX,Diafenthiuron (226)+TX,Dialifos (1042)+TX,Diazinon (227)+TX,Dichlofluanid (230)+TX,DDVP (236)+TX,Dicliphos (alias)+TX,Dicofol (242)+TX,Carbicron (243)+TX,Gram (1071)+TX everywhere,BFPO (1081)+TX,Rogor (262)+TX,Diformazan polynactin (alias) (653)+TX,Dinitrocyclohexylphenol (1089)+TX,Dinitrocyclohexylphenol (dinex-diclexine) (1089)+TX,Dinobuton (269)+TX,Dinocap (270)+TX,Dinocap -4 [CCN]+TX,Dinocap -6 [CCN]+TX,Dinitro ester (1090)+TX,Dinopenton (1092)+TX,Nitre monooctyl ester (1097)+TX,Dinoterbon (1098)+TX,Dioxathion (1102)+TX,Diphenyl sulphone (DPS) (IUPAC titles) (1103)+TX,Abstinyl (alias) [CCN]+TX,Disulfoton (278)+TX,DNOC(282)+TX,Benzene oxycetylene mite (1113)+TX,Doractin (alias) [CCN]+TX,5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX,Endothion (1121)+TX,EPN(297)+TX,According to general rhzomorph (alias) [CCN]+TX,Ethodan (309)+TX,Ethoate methyl (1134)+TX,Etoxazole (320)+TX,Etrimfos (1142)+TX,Fenazaflor (1147)+TX,Fenazaquin (328)+TX,Fenbutatin oxide (330)+TX,Fenothiocarb (337)+TX,Fenpropathrin (342)+TX,Tebufenpyrad (alias)+TX,Fenpyroximate (345)+TX,Fenson (1157)+TX,Fluorine nitre diphenylamines (1161)+TX,Fenvalerate (349)+TX,Ethiprole (354)+TX,Fluacrypyrim (360)+TX,Fluazuron (1166)+TX,Fluorine mite thiophene (1167)+TX,Flucycloxuron (366)+TX,Flucythrinate (367)+TX,Fluenyl (1169)+TX,Flufenoxuron (370)+TX,Flumethrin (372)+TX,Fluoraracide (1174)+TX,Taufluvalinate (1184)+TX,FMC1137 (research code) (1185)+TX,Carzol (405)+TX,Carzol SP (405)+TX,Formothion (1192)+TX,Amine first prestige (1193)+TX,γ-HCH(430)+TX,Glyodin (1205)+TX,Halfenprox (424)+TX,Heptene ether (432)+TX,Hexadecane basic ring carboxylate (IUPAC/ chemical abstracts name) (1216)+TX,Hexythiazox (441)+TX,Iodomethane (IUPAC titles) (542)+TX,Isocarbophos (alias) (473)+TX,Isopropyl O- (Methoxyamino thiophosphoryl) salicylate (IUPAC titles) (473)+TX,Olivomitecidin (alias) [CCN]+TX,Jasmolin I (696)+TX,Jasmolin ii (696)+TX,Iodfenphos (1248)+TX,Lindane (430)+TX,Lufenuron (490)+TX,Malathion (492)+TX,Benzyl malononitrile (1254)+TX,Afos (502)+TX,Mephosfolan (1261)+TX,Mesulfen (alias) [CCN]+TX,Methacrifos (1266)+TX,Acephatemet (527)+TX,Methidathion (529)+TX,Methiocarb (530)+TX,Methomyl (531)+TX,Bromomethane (537)+TX,MTMC (550)+TX,Menite (556)+TX,Mexacarbate (1290)+TX,Milbemectin (557)+TX,Polynactin oxime (alias) [CCN]+TX,Mipafox (1293)+TX,Azodrin (561)+TX,Morphothion (1300)+TX,Moxidectin (alias) [CCN]+TX,2-dichloroethylk dimethyl phosphate (567)+TX,NC-184 (compound code)+TX,NC-512 (compound code)+TX,Fluorine mosquito spirit (1309)+TX,Nikkomycin (alias) [CCN]+TX,Nitrilacarb (1313)+TX,Nitrilacarb 1：1 zinc chloride complex compound (1313)+TX,NNI-0101 (compound code)+TX,NNI-0250 (compound code)+TX,Omethoate (594)+TX,Oxamyl (602)+TX,Sub- Thiometan (1324)+TX,Disystom-s (1325)+TX,pp′-DDT(219)+TX,Parathion (615)+TX,Permethrin (626)+TX,Oil (alias) (628)+TX,Phenkapton (1330)+TX,Phenthoate dimephenthoate cidial (631)+TX,Thimet (636)+TX,Phosalone (637)+TX,Phosfolan (1338)+TX,Phosmet (638)+TX,Phosphamidon (639)+TX,Phoxim (642)+TX,Pirimiphos-methyl (652)+TX,Citicide (traditional title) (1347)+TX,Polynactin (alias) (653)+TX,Go out mite alcohol (1350)+TX,Profenofos (662)+TX,Promacyl (1354)+TX,Propargite (671)+TX,Propetamphos (673)+TX,Arprocarb (678)+TX,Prothidathion (1360)+TX,Prothoate (1362)+TX,Pyrethrins I (696)+TX,Chrysanthemumdicarboxylic acid monomethyl ester pyrethrolone ester (696)+TX,Pyrethrin (696)+TX,Pyridaben (699)+TX,Pyridaphethione (701)+TX,Pyrimidifen (706)+TX,Diothyl (1370)+TX,Quinalphos (711)+TX,Quinoline tears good fortune (1381)+TX,R-1492 (research code) (1382)+TX,RA-17 (research code) (1383)+TX,Rotenone (722)+TX,Schradane (1389)+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,SI-0009 (compound code)+TX,Sophamide (1402)+TX,Envidor (738)+TX,Spiromesifen (739)+TX,SSI-121 (research code) (1404)+TX,Sulfiram (alias) [CCN]+TX,Sulfluramid (750)+TX,Sulfotep (753)+TX,Sulfur (754)+TX,SZI-121 (research code) (757)+TX,τ-taufluvalinate (398)+TX,Tebufenpyrad (763)+TX,TEPP(1417)+TX,Terbam (alias)+TX,Ravap (777)+TX,Tetradiphon (786)+TX,Polynactin (alias) (653)+TX,Mite killing thioether (1425)+TX,Thiafenox (alias)+TX,Talcord (1431)+TX,Thiofanox (800)+TX,Thiometon (801)+TX,Eradex (1436)+TX,Su Li rhzomorphs (alias) [CCN]+TX,Triamiphos (1441)+TX,Benzene thiophene mite (1443)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Metrifonate (824)+TX,The phosphorus of chlorobenzene second third (1455)+TX,One first polynactin (alias) (653)+TX,Vamidothion (847)+TX,Fluorine pyrazoles worm [CCN] and YI-5302 (compound code)+TX,
The algicide being selected from the group：Bethoxazin [CCN]+TX, two cupric octoates (IUPAC titles) (170)+TX, copper sulphate (172)+TX, cybutryne [CCN]+TX, dihydro naphthoquinones (1052)+TX, double hydrogen phenol (232)+TX, bacterium polyacid (295)+TX, fentin (347)+TX, white lime [CCN]+TX, Dithane A40 (566)+TX, quinoclamine (714)+TX, quinone duckweed amine (1379)+TX, Simanex (730)+TX, fentin acetate (IUPAC titles) (347) and fentin hydrochloride (IUPAC titles) (347)+TX,
The anthelmintic being selected from the group：AVM (1)+TX, Ruelene (1011)+TX, doractin (alias) [CCN]+TX, emaricin (291)+TX, emaricin benzoic ether (291)+TX, according to general rhzomorph (alias) [CCN]+TX, Olivomitecidin (alias) [CCN]+TX, polynactin oxime (alias) [CCN]+TX, moxidectin (alias) [CCN]+TX, piperazine [CCN]+TX, selamectin (alias) [CCN]+TX, pleocidin (737) and thiophanate (1435)+TX
The avicide being selected from the group：Chloralose (127)+TX, endrin (1122)+TX, Entex (346)+TX, pyridine -4- amine (IUPAC titles) (23) and strychnine (745)+TX,
The bactericide being selected from the group：1- hydroxyls -1H- pyridine -2- thioketones (IUPAC titles) (1222)+TX, 4- (quinoxaline -2- bases amino) benzsulfamide (IUPAC titles) (748)+TX, 8-hydroxyquinoline sulfate (446)+TX, bronopol (97)+TX, two cupric octoates (IUPAC titles) (170)+TX, Kocide SD (IUPAC titles) (169)+TX, cresols [CCN]+TX, double hydrogen phenol (232)+TX, pyrrole bacterium sulphur (1105)+TX, many enemy bacterium (1112)+TX, fenaminosulf (1144)+TX, formaldehyde (404)+TX, conotrane (alias) [CCN]+TX, kasugarnycin (483)+TX, kasugamycin hydrochloride hydrate (483)+TX, two (dimethyl dithiocarbamate) nickel (IUPAC titles) (1308)+TX, trichloromethyl pyridine (580)+TX, octhilinone (590)+TX, oxolinic acide (606)+TX, terramycin (611)+TX, oxyquinoline potassium sulfate (446)+TX, probenazole (658)+TX, streptomysin (744)+TX, streptomysin sesquisulfate (744)+TX, tecloftalam (766)+TX and merthiolate (alias) [CCN]+TX,
The biological reagent being selected from the group：Adoxophyes moth PuGV (alias) (12)+TX,Jia Teluo (alias) (13)+TX,Predatory Mites (alias) (19)+TX,Celery looper nucleopolyhedrosis virus (alias) (28)+TX,Former cherry wing tassel chalcid fly (Anagrus atomus) (alias) (29)+TX,Aphid parasitic wasp (alias) (33)+TX,Cotten aphid parasitic wasp (alias) (34)+TX,Eat aphid cecidomyiia (alias) (35)+TX,Autographa californica nuclear polyhedrosis virus (alias) (38)+TX,Bacillus firmus (alias) (48)+TX,Bacillus sphaericus (scientific name) (49)+TX,Dipel (scientific name) (51)+TX,Dipel a. (scientific name) (51)+TX,Dipel I. (scientific name) (51)+TX,Dipel Japan subspecies (scientific name) (51)+TX,Dipel k. (scientific name) (51)+TX,Dipel t. (scientific name) (51)+TX,Beauveria bassiana (alias) (53)+TX,Muscardine (alias) (54)+TX,Lacewing (alias) (151)+TX,Cryptolaemus montrouzieri (alias) (178)+TX,Carpocapsa pomonella granulosis virus (alias) (191)+TX,Dacnusa sibirica (alias) (212)+TX,Diglyphus isaea (alias) (254)+TX,Encarsia formosa (scientific name) (293)+TX,Eretmocerus SP (alias) (300)+TX,Corn earworm nucleopolyhedrosis virus (alias) (431)+TX,Heterorhabditis bacteriophora-NJ and H.megidis (alias) (433)+TX,Assemble considerable ladybug (alias) (442)+TX,Tangerine powder scale insect parasitic wasp (alias) (488)+TX,Fleahopper (alias) (491)+TX,Lopper worm nucleopolyhedrosis virus (alias) (494)+TX,Metaphycushelvolus (alias) (522)+TX,Yellowish green green muscardine fungus (scientific name) (523)+TX,Metarhizium anisopliae var. Anisopliae (scientific name) (523)+TX,Neodiprion sertifer nucleopolyhedrosis virus and reddish tone pine bark procyanidins nucleopolyhedrosis virus (alias) (575)+TX,Minute pirate bugs (alias) (596)+TX,Paecilomyces fumosoroseus (alias) (613)+TX,Plant mite (alias) (644)+TX catches in Chile,Many nucleocapsid nucleopolyhedrosis virus (scientific name) (the 741)+TX of beet armyworm,March fly nematode (alias) (742)+TX,Nematode Steinernema carpocapsae (alias) (742)+TX,Steinernema feltiae (alias) (742)+TX,Form nematode (Steinernema glaseri) (alias) (742)+TX,Steinernemariobrave (alias) (742)+TX,Steinernema riobravis (alias) (742)+TX,Mole cricket Steinernema Carpocapsae (Steinernema scapterisci) (alias) (742)+TX,Steinernema Carpocapsae (alias) (742)+TX,Trichogramma (alias) (826)+TX,West it is blind walk mite (alias) (844) and Verticillium lecanii (alias) (848)+TX,
The soil sterilants being selected from the group：Iodomethane (IUPAC titles) (542) and bromomethane (537)+TX,
The chemosterilants being selected from the group：Apholate [CCN]+TX, pyrrole thiophene north (bisazir) (alias) [CCN]+TX, sulphur butane (alias) [CCN]+TX, diflubenzuron (250)+TX, dimatif (alias) [CCN]+TX, hemel [CCN]+TX, hempa [CCN]+TX, metepa [CCN]+TX, Metapside [CCN]+TX, aphamide piperazine [CCN]+TX, infertile pyridine [CCN]+TX, penfluron (alias) [CCN]+TX, tepa [CCN]+TX, thio hempa (alias) [CCN]+TX, thio-tepa (alias) [CCN]+TX, tretamine (alias) [CCN] and uredepa (alias) [CCN]+TX,
It is selected from the group the insect pheromone of material：(E)-decyl- 5- alkene -1- yl acetates (IUPAC titles) (222)+TX with (E)-decyl- 5- alkene -1- alcohol,(E)-ten three -4- alkene -1- yl acetates (IUPAC titles) (829)+TX,(E) -6- methyl hept-2-ene" -4- alcohol (IUPAC titles) (541)+TX,(E,Z)-ten four -4,10- diene -1- yl acetates (IUPAC titles) (779)+TX,(Z)-ten two -7- alkene -1- yl acetates (IUPAC titles) (285)+TX,(Z)-ten six -11- olefine aldehydrs (IUPAC titles) (436)+TX,(Z)-ten six -11- alkene -1- yl acetates (IUPAC titles) (437)+TX,(Z)-ten six -13- alkene -11- alkynes -1- yl acetates (IUPAC titles) (438)+TX,(Z)-two ten -13- alkene -10- ketone (IUPAC titles) (448)+TX,(Z)-ten four -7- alkene -1- aldehyde (IUPAC titles) (782)+TX,(Z)-ten four -9- alkene -1- alcohol (IUPAC titles) (783)+TX,(Z)-ten four -9- alkene -1- yl acetates (IUPAC titles) (784)+TX,(7E,9Z)-ten two -7,9- diene -1- yl acetates (IUPAC titles) (283)+TX,(9Z,11E)-ten four -9,11- diene -1- yl acetates (IUPAC titles) (780)+TX,(9Z,12E)-ten four -9,12- diene -1- yl acetates (IUPAC titles) (781)+TX,- 1- the alkene of 14- methyl 18 (IUPAC titles) (545)+TX,4- methyl nonyl- 5- alcohol (IUPAC titles) (544)+TX with 4- methyl nonyl- 5- ketone,α-ripple bark beetle (alias) [CCN]+TX,Western pine bark beetle assembly pheromone (alias) [CCN]+TX,Pherocon CM (codlelure) (alias) [CCN]+TX,Pherocon CM (codlemone) (alias) (167)+TX,Cue-lure (alias) (179)+TX,Disparmone (277)+TX,12 .-8- alkene -1- yl acetates (IUPAC titles) (286)+TX,12-9- alkene-1- yl acetates (IUPAC titles) (287)+TX,12-8+TX,10- diene -1- yl acetates (IUPAC titles) (284)+TX,Lesser grain borer aggregation pheromone (alias) [CCN]+TX,4- methyloctanoic acids ethyl ester (IUPAC titles) (317)+TX,Eugenol (alias) [CCN]+TX,Dendroctonus frontalis assembly pheromone (alias) [CCN]+TX,Gossyplure (alias) (420)+TX,Grandemone (421)+TX,Grandemone I (alias) (421)+TX,Grandemone II (alias) (421)+TX,Grandemone III (alias) (421)+TX,Grandemone IV (alias) (421)+TX,Hexalure [CCN]+TX,Bark beetle dienol (alias) [CCN]+TX,Bark beetle enol (alias) [CCN]+TX,Chafer gyplure (alias) (481)+TX,Secret note wood bark beetle element (alias) [CCN]+TX,Vertical spy lures (litlure) (alias) [CCN]+TX,Sieve, which is caught, lures (alias) [CCN]+TX,Medlure [CCN]+TX,Megatomoic acid (alias) [CCN]+TX,Allylveratrole (alias) (540)+TX,Muscalure (563)+TX,Ten eight -2,13- diene -1- yl acetates (IUPAC titles) (588)+TX,Ten eight -3,13- diene -1- yl acetates (IUPAC titles) (589)+TX,He Kangbi (alias) [CCN]+TX,Oryctalure (alias) (317)+TX,Fei Lekang (alias) [CCN]+TX,Siglure [CCN]+TX,Sordidin (alias) (736)+TX,Sulcatol (sulcatol) (alias) [CCN]+TX,14-11- alkene-1- yl acetates (IUPAC titles) (785)+TX,Spy lures ketone (839)+TX,Spy lures ketone A (alias) (839)+TX,Spy lures ketone B1(alias) (839)+TX, spy lure ketone B2(alias) (839)+TX, spy lure ketone C (alias) (839) and trunc-call (alias) [CCN]+TX,
It is selected from the group the insect repellent of material：2- (octylsulfo) ethanol (IUPAC titles) (591)+TX, dihydropyrone (933)+TX, butoxy (polypropylene glycol) (936)+TX, dibutyl adipate (IUPAC titles) (1046)+TX, dibutyl phthalate (1047)+TX, dibutyl succinate (IUPAC titles) (1048)+TX, Metadelphene [CCN]+TX, dimethyl carbate [CCN]+TX, dimethyl phthalate [CCN]+TX, Rutgers 612 (1137)+TX, hexamid [CCN]+TX, first quinoline fourth (1276)+TX, the new decyl amide of methyl [CCN]+TX, oxamic acid ester [CCN] and picaridin [CCN]+TX,
It is selected from the group the insecticide of material：1,The chloro- 1- nitroethanes of 1- bis- (IUPAC/ chemical abstracts name) (1058)+TX,1,1- bis- chloro- 2,2- bis- (4- ethylphenyls) ethane (IUPAC titles) (1056)+TX,1,2- dichloropropanes (IUPAC/ chemical abstracts name) (1062)+TX,With 1,The 1 of 3- dichloropropylenes,2- dichloropropanes (IUPAC titles) (1063)+TX,The bromo- 2- chloroethanes of 1- (IUPAC/ chemical abstracts name) (916)+TX,2,2,The chloro- 1- (3 of 2- tri-,4- dichlorophenyls) ethylhexoate (IUPAC titles) (1451)+TX,2,2- bis- dichloroethylene 2- ethylsulfinyl ethyl-methyls phosphate (IUPAC titles) (1066)+TX,2-(1,The amyl- 2- yls of 3- dithia rings) pheiiyldimetliyl carbamate (IUPAC/ chemical abstracts name) (1109)+TX,2- (2- Butoxyethoxies) ethylenebis dithiocarbamate cyanate (IUPAC/ chemical abstracts name) (935)+TX,2-(4,5- dimethyl -1,3- dioxolan 2 yls) phenol methylcarbamate (IUPAC/ chemical abstracts name) (1084)+TX,2- (4- chloro- 3,5- xylyls epoxide) ethanol (IUPAC titles) (986)+TX,2- chlorovinyls diethylphosphate (IUPAC titles) (984)+TX,2- imidazolones (IUPAC titles) (1225)+TX,2- isovaleryl indane -1,3- diketone (IUPAC titles) (1246)+TX,2- methyl (Propargyl) aminophenyl methyl carbamate (IUPAC titles) (1284)+TX,The thio cyanato- ethyl laurates of 2- (IUPAC titles) (1433)+TX,The bromo- 1- chlorine propyl- 1- alkene of 3- (IUPAC titles) (917)+TX,3- methyl isophthalic acids-Phenylpyrazole -5- bases dimethylcarbamate (IUPAC titles) (1283)+TX,4- methyl (Propargyl) amino -3,5- xylyls methyl carbamate (IUPAC titles) (1285)+TX,5,5- dimethyl -3- epoxides hexamethylene -1- alkenyls dimethylcarbamate (IUPAC titles) (1085)+TX,AVM (1)+TX,Orthene (2)+TX,Acetamiprid (4)+TX,Acethion (alias) [CCN]+TX,Acetyl worm nitrile [CCN]+TX,Acrinathrin (9)+TX,Acrylonitrile (IUPAC titles) (861)+TX,Alanycarb (15)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,Drinox (864)+TX,Allethrin (17)+TX,Chitinase presses down thing (allosamidin) (alias) [CCN]+TX,Allyxycarb (866)+TX,α-cypermethrin (202)+TX,α-ecdysone (alias) [CCN]+TX,Aluminum phosphate (640)+TX,Amidithion (870)+TX,amidothioate(872)+TX,Aminocarb (873)+TX,Citram (875)+TX,Citram binoxalate (875)+TX,Amitraz (24)+TX,Anabasine (877)+TX,Ai Saidasong (883)+TX,AVI382 (compound code)+TX,AZ60541 (compound code)+TX,Nimbin (alias) (41)+TX,Azamethiphos (42)+TX,Azinphos ethyl (44)+TX,Azinphos-methyl (45)+TX,Alamos (889)+TX,Bacillus thuringiensis crystalline substance toxalbumin (alias) (52)+TX,Hexafluoro barium silicate (alias) [CCN]+TX,Solbar (IUPAC/ chemical abstracts name) (892)+TX,Barthrin [CCN]+TX,Bayer22/190 (research code) (893)+TX,Bayer22408 (research code) (894)+TX,Ficam (58)+TX,Benfuracard micro (60)+TX,Bensultap (66)+TX,β-cyfloxylate (194)+TX,β-cypermethrin (203)+TX,Bifenthrin (76)+TX,Bioallethrin (78)+TX,Bioallethrin S- cyclopentenyls isomers (alias) (79)+TX,bioethanomethrin[CCN]+TX,Biopermethrin (908)+TX,Bioresmethrin (80)+TX,Two (2- chloroethyls) ether (IUPAC titles) (909)+TX,Bistrifluron (83)+TX,Borax (86)+TX,Brofenxalerate (alias)+TX,Bromobenzene alkene phosphorus (914)+TX,Bromocyclne (918)+TX,Bromo- DDT (alias) [CCN]+TX,Bromophos (920)+TX,Rilariol (921)+TX,Conjunction must prestige (924)+TX,Buprofezin (99)+TX,Butacarb (926)+TX,Special Pyrimitate (927)+TX,Butocarboxim (103)+TX,Butyl ester phosphine (932)+TX,Butanone sulfone prestige (104)+TX,Butyl pyridaben (alias)+TX,Cadusafos (109)+TX,Calcium arsenate [CCN]+TX,Cyanogas (444)+TX,Lime sulfur (IUPAC titles) (111)+TX,Toxaphene (941)+TX,Sok (943)+TX,Carbaryl (115)+TX,Carbofuran (118)+TX,Carbon disulfide (IUPAC/ chemical abstracts name) (945)+TX,Carbon tetrachloride (IUPAC titles) (946)+TX,Carbophenothion (947)+TX,Carbosulfan (119)+TX,Padan (123)+TX,Padan's hydrochloride (123)+TX,Cevadilla (alias) (725)+TX,Chlorbicyclen (960)+TX,Niran (128)+TX,Kepone (963)+TX,Spanon (964)+TX,Chlordimeform-hydrochloride (964)+TX,Chlorethoxyfos (129)+TX,Chlorfenapyr (130)+TX,Chlorfenviphos (131)+TX,Chlorfluazuron (132)+TX,Chlormephos (136)+TX,Chloroform [CCN]+TX,Chloropicrin (141)+TX,Chlorophoxim (989)+TX,Chlorine pyrazoxon (990)+TX,Chlopyrifos (145)+TX,Chlorpyrifos-methyl (146)+TX,Actellic (994)+TX,Ring tebufenozide (150)+TX,Cinerin (696)+TX,Cinerin I (696)+TX,II cinerin II (696)+TX,Cis-resmethrin (alias)+TX,Bioresmethrin (80)+TX,Cyhalothrin (alias)+TX,Cloethocarb (999)+TX,Closantel (alias) [CCN]+TX,Clothianadin (165)+TX,Paris green [CCN]+TX,Copper arsenate [CCN]+TX,Copper oleate [CCN]+TX,Resistox (174)+TX,Dithion (1006)+TX,Crotonocyl toluidines (alias) [CCN]+TX,Crotoxyphos (1010)+TX,Ruelene (1011)+TX,Ice crystal (alias) (177)+TX,CS708 (research code) (1012)+TX,Surecide (1019)+TX,Cynock (184)+TX,Cyanthoate (1020)+TX,Cyclethrin [CCN]+TX,Cycloprothrin (188)+TX,Cyfloxylate (193)+TX,Lambda-cyhalothrin (196)+TX,Cypermethrin (201)+TX,Cyphenothrin (206)+TX,Cyromazine (209)+TX,Cythioate (alias) [CCN]+TX,(R)-4-isopropenyl-1-methyl-1-cyclohexene (alias) [CCN]+TX,D- tetramethrins (alias) (788)+TX,DAEP(1031)+TX,Dazomet (216)+TX,DDT(219)+TX,One first Furadan (1034)+TX,Decis (223)+TX,Demephion (1037)+TX,Demephion-O (1037)+TX,Demephion-S (1037)+TX,Demeton (1038)+TX,Demeton-methyl (224)+TX,Demeton-O (1038)+TX,Demeton-methyl-O (224)+TX,Demeton-S (1038)+TX,Demeton-methyl-S (224)+TX,Metilomerkaptofosoksid (1039)+TX,Diafenthiuron (226)+TX,Dialifos (1042)+TX,Nellite (1044)+TX,Diazinon (227)+TX,Di-captan (1050)+TX,Dichlofenthion (1051)+TX,DDVP (236)+TX,Dicliphos (alias)+TX,Dicresyl (alias) [CCN]+TX,Carbicron (243)+TX,CGA 183893 (244)+TX,Dieldrite (1070)+TX,Diethyl 5- methylpyrazole -3- bases phosphate (IUPAC titles) (1076)+TX,Diflubenzuron (250)+TX,Neutraphylline (dilor) (alias) [CCN]+TX,Dimefluthrin [CCN]+TX,BFPO (1081)+TX,Dimetan (1085)+TX,Rogor (262)+TX,Dimethrin (1083)+TX,Dimethylvinphos (265)+TX,Dimetilan (1086)+TX,Dinitrocyclohexylphenol (1089)+TX,Dinitrocyclohexylphenol (dinex-diclexine) (1089)+TX,Dinoprop (1093)+TX,Dinosam (1094)+TX,Dinoseb (1095)+TX,MTI-446 (271)+TX,Difenolan (1099)+TX,Salithion (1100)+TX,Elacron (1101)+TX,Dioxathion (1102)+TX,Disulfoton (278)+TX,Thiapyran phosphorus (1108)+TX,DNOC(282)+TX,Doractin (alias) [CCN]+TX,DSP(1115)+TX,β-ecdysone (alias) [CCN]+TX,EI1642 (research code) (1118)+TX,Emaricin (291)+TX,Emaricin benzoic ether (291)+TX,EMPC(1120)+TX,Empenthrin (292)+TX,5a,6,9,9a-hexahydro-6,9-methano-2,4 (294)+TX,Endothion (1121)+TX,Endrin (1122)+TX,EPBP(1123)+TX,EPN(297)+TX,Protect children ether (1124)+TX,According to general rhzomorph (alias) [CCN]+TX,S- fenvalerates (302)+TX,Etaphos (alias) [CCN]+TX,Ethiofencarb (308)+TX,Ethodan (309)+TX,Ethiprole (310)+TX,Ethoate methyl (1134)+TX,Phonamiphos (312)+TX,Ethyl formate (IUPAC titles) [CCN]+TX,Perthane (alias) (1056)+TX,Bromofume (316)+TX,Dichloroethanes (chemical name) (1136)+TX,Oxirane [CCN]+TX,Ethofenprox (319)+TX,Etrimfos (1142)+TX,EXD(1143)+TX,Famphur (323)+TX,Fenamiphos (326)+TX,Fenazaflor (1147)+TX,Nankor (1148)+TX,Ethylbenzene prestige (1149)+TX,Fenfluthrin (1150)+TX,Fenifrothion (335)+TX,Bassa (336)+TX,fenoxacrim(1153)+TX,Fenoxycarb (340)+TX,Fenpirithrin (1155)+TX,Fenpropathrin (342)+TX,Tebufenpyrad (alias)+TX,Fensulfothion (1158)+TX,Entex (346)+TX,Entex [CCN]+TX,Fenvalerate (349)+TX,Ethiprole (354)+TX,Flonicamid (358)+TX,Fluorobenzene diamines (CAS registration numbers：272451-65-7)+TX,Grand (the 1168)+TX of the double benzene of fluorine fluorine,Flucycloxuron (366)+TX,Flucythrinate (367)+TX,Fluenyl (1169)+TX,flufenerim[CCN]+TX,Flufenoxuron (370)+TX,Trifluoro ethofenprox (1171)+TX,Flumethrin (372)+TX,Taufluvalinate (1184)+TX,FMC1137 (research code) (1185)+TX,Fonofos (1191)+TX,Carzol (405)+TX,Carzol SP (405)+TX,Formothion (1192)+TX,Amine first prestige (1193)+TX,Fosmethilan (1194)+TX,Chlorpyrifos-methyl (1195)+TX,Lythidathion (408)+TX,Fosthietan (1196)+TX,Furathiocarb (412)+TX,Furethrin (1200)+TX,Gamma-cyhalothrin (197)+TX,γ-HCH(430)+TX,Guanoctine (422)+TX,Biguanides acetate (422)+TX,GY-81 (research code) (423)+TX,Halfenprox (424)+TX,Chlorine tebufenozide (425)+TX,HCH(430)+TX,HEOD(1070)+TX,Heptachlor (1211)+TX,Heptene ether (432)+TX,Speed kills sulphur phosphorus [CCN]+TX,HEXAFLUMURON (439)+TX,HHDN(864)+TX,Hydramethylnon Bait (443)+TX,Hydrogen cyanide (444)+TX,Hydroprene (445)+TX,Quinoline prestige (1223)+TX,Imidacloprid (458)+TX,Miaow alkynes chrysanthemum ester (460)+TX,Indoxacarb (465)+TX,Iodomethane (IUPAC titles) (542)+TX,IPSP(1229)+TX,Isazofos (1231)+TX,Telodrin (1232)+TX,Isocarbophos (alias) (473)+TX,Isodrin (1235)+TX,Isofenphos (1236)+TX,Isolan (1237)+TX,Mobucin (472)+TX,Isopropyl O- (Methoxyamino thiophosphoryl) salicylate (IUPAC titles) (473)+TX,Isoprothiolane (474)+TX,Isothioate (1244)+TX,Isoxathion (480)+TX,Olivomitecidin (alias) [CCN]+TX,Jasmolin I (696)+TX,Jasmolin ii (696)+TX,Iodfenphos (1248)+TX,Juvenile hormone I (alias) [CCN]+TX,Juvenile hormone II (alias) [CCN]+TX,Juvenile hormone III (alias) [CCN]+TX,Ke Laifan (1249)+TX,Kinoprene (484)+TX,λ-lambda-cyhalothrin (198)+TX,Lead arsenate [CCN]+TX,lepimectin(CCN)+TX,Leptophos (1250)+TX,Lindane (430)+TX,Pyridine worm phosphorus (1251)+TX,Lufenuron (490)+TX,Lythidathion (1253)+TX,Between cumenyl methyl carbamate (IUPAC titles) (1014)+TX,Magnesium phosphide (IUPAC titles) (640)+TX,Malathion (492)+TX,Benzyl malononitrile (1254)+TX,Mazidox (1255)+TX,Afos (502)+TX,Mecarphon (1258)+TX,Menazon (1260)+TX,Mephosfolan (1261)+TX,Calogreen (513)+TX,First oxydemeton_methyl (1263)+TX,metaflumizone(CCN)+TX,Hundred mu of (519)+TX,Hundred mu-sylvite (alias) (519)+TX,Hundred mu-sodium salt (519)+TX,Methacrifos (1266)+TX,Acephatemet (527)+TX,Methanesulfonyl fluoride (IUPAC/ chemical abstracts name) (1268)+TX,Methidathion (529)+TX,Methiocarb (530)+TX,Butenylamine phosphorus (1273)+TX,Methomyl (531)+TX,Methoprene (532)+TX,First quinoline fourth (1276)+TX,Methothrin (alias) (533)+TX,Methoxychlor (534)+TX,Methoxyfenozide (535)+TX,Bromomethane (537)+TX,Methyl-isorhodanate (543)+TX,Methyl chloroform (alias) [CCN]+TX,Dichloromethane [CCN]+TX,Metofluthrin [CCN]+TX,MTMC (550)+TX,Metoxadiazone (1288)+TX,Menite (556)+TX,Mexacarbate (1290)+TX,Milbemectin (557)+TX,Polynactin oxime (alias) [CCN]+TX,Mipafox (1293)+TX,Mirex (1294)+TX,Azodrin (561)+TX,Morphothion (1300)+TX,Moxidectin (alias) [CCN]+TX,How peptide phosphorus (alias) [CCN]+TX,2-dichloroethylk dimethyl phosphate (567)+TX,Naphthalene (IUPAC/ chemical abstracts name) (1303)+TX,NC-170 (research code) (1306)+TX,NC-184 (compound code)+TX,Nicotine (578)+TX,Nicotine sulfate (578)+TX,Fluorine mosquito spirit (1309)+TX,Nitenpyram (579)+TX,Nithiazine (1311)+TX,Nitrilacarb (1313)+TX,Nitrilacarb 1：1 zinc chloride complex compound (1313)+TX,NNI-0101 (compound code)+TX,NNI-0250 (compound code)+TX,Ninicotine (traditional title) (1319)+TX,Novaluron (585)+TX,Noviflumuron (586)+TX,O-2,The chloro- 4- iodine substituted phenyls O- ethyl diethyldithiocarbamates thiophosphates of 5- bis- (IUPAC titles) (1057)+TX,O,O- diethyl O-4- methyl -2- oxos -2H- chromene -7- bases thiophosphate (IUPAC titles) (1074)+TX,O,O- diethyl O-6- methyl-2-propyl pyrimidine-4-yls thiophosphate (IUPAC titles) (1075)+TX,O,O,O′,The thiopyrophosphate of O '-tetrapropyl two (IUPAC titles) (1424)+TX,Oleic acid (IUPAC titles) (593)+TX,Omethoate (594)+TX,Oxamyl (602)+TX,Metilomerkaptofosoksid (609)+TX,Sub- Thiometan (1324)+TX,Disystom-s (1325)+TX,pp′-DDT(219)+TX,Paracide [CCN]+TX,Parathion (615)+TX,Parathion-methyl (616)+TX,Penfluron (alias) [CCN]+TX,Pentachlorophenol (623)+TX,Pentachlorophenyl laurate (IUPAC titles) (623)+TX,Permethrin (626)+TX,Oil (alias) (628)+TX,PH60-38 (research code) (1328)+TX,Phenkapton (1330)+TX,Phenothrin (630)+TX,Phenthoate dimephenthoate cidial (631)+TX,Thimet (636)+TX,Phosalone (637)+TX,Phosfolan (1338)+TX,Phosmet (638)+TX,Nichlorfos (1339)+TX,Phosphamidon (639)+TX,Hydrogen phosphide (IUPAC titles) (640)+TX,Phoxim (642)+TX,Phoxiom_methyl (1340)+TX,The phonetic phosphorus of methylamine (1344)+TX,Aphox (651)+TX,Ethyl-pyrimidine phosphorus (1345)+TX,Pirimiphos-methyl (652)+TX,Many chlorine bicyclopentadiene isomers (IUPAC titles) (1346)+TX,Citicide (traditional title) (1347)+TX,Potassium arsenite [CCN]+TX,Potassium thiocyanate [CCN]+TX,Prallethrin (655)+TX,Precocene I (alias) [CCN]+TX,Precocene II (alias) [CCN]+TX,Precocene III (alias) [CCN]+TX,Acid amides Diothyl (1349)+TX,Profenofos (662)+TX,Third Flumethrin [CCN]+TX,Promacyl (1354)+TX,Carbamult (1355)+TX,Kayaphos (1356)+TX,Propetamphos (673)+TX,Arprocarb (678)+TX,Prothidathion (1360)+TX,Toyodan (686)+TX,Prothoate (1362)+TX,Propyl benzene hydrocarbon chrysanthemum ester [CCN]+TX,Pymetrozine (688)+TX,Pyraclofos (689)+TX,Pyrazophos (693)+TX,Anti- Chryson (1367)+TX,Pyrethrins I (696)+TX,Chrysanthemumdicarboxylic acid monomethyl ester pyrethrolone ester (696)+TX,Pyrethrin (696)+TX,Pyridaben (699)+TX,Pyridalyl (700)+TX,Pyridaphethione (701)+TX,Pyrimidifen (706)+TX,Diothyl (1370)+TX,Nylar (708)+TX,Quassia (alias) [CCN]+TX,Quinalphos (711)+TX,Methyl quinalphos (1376)+TX,High (the 1380)+TX of quinoline match,Quinoline tears good fortune (1381)+TX,R-1492 (research code) (1382)+TX,Iodo-ether salicylamine (alias) [CCN]+TX,Resmethrin (719)+TX,Rotenone (722)+TX,RU15525 (research code) (723)+TX,RU25475 (research code) (1386)+TX,Ryanicide (alias) (1387)+TX,Ryanicide (traditional title) (1387)+TX,Jervine (alias) (725)+TX,Schradane (1389)+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,SI-0009 (compound code)+TX,SI-0205 (compound code)+TX,SI-0404 (compound code)+TX,SI-0405 (compound code)+TX,Silafluofene (728)+TX,SN72129 (research code) (1397)+TX,Sodium arsenite [CCN]+TX,Cymag (444)+TX,Sodium fluoride (IUPAC/ chemical abstracts name) (1399)+TX,Sodium hexafluorisilicate (1400)+TX,Pentachlorobenzene sodium oxide molybdena (623)+TX,Sodium selenate (IUPAC titles) (1401)+TX,Thiocyanic acid sodium [CCN]+TX,Sophamide (1402)+TX,Pleocidin (737)+TX,Spiromesifen (739)+TX,Spiral shell worm ethyl ester (spirotetrmat) (CCN)+TX,Grand (the 746)+TX of sulphur phenylate,The grand sodium salt of sulphur phenylate (746)+TX,Sulfluramid (750)+TX,Sulfotep (753)+TX,Vikane (756)+TX,Sulprofos (1408)+TX,Tar (alias) (758)+TX,τ-taufluvalinate (398)+TX,Tazimcarb (1412)+TX,TDE(1414)+TX,Tebufenozide (762)+TX,Tebufenpyrad (763)+TX,Butyl pyrimidine phosphorus (764)+TX,Fluorobenzene urea (768)+TX,Tefluthrin (769)+TX,Swebate (770)+TX,TEPP(1417)+TX,Terallethrin (1418)+TX,Terbam (alias)+TX,Terbufos (773)+TX,Tetrachloroethanes [CCN]+TX,Ravap (777)+TX,Tetramethrin (787)+TX,θ-cypermethrin (204)+TX,Thiacloprid (791)+TX,Thiafenox (alias)+TX,Diacloden (792)+TX,Thiophene chlorine phosphorus (1428)+TX,Talcord (1431)+TX,Thiocyclam (798)+TX,Thiocyclam binoxalate (798)+TX,Thiodicarb (799)+TX,Thiofanox (800)+TX,Thiometon (801)+TX,Thionazin (1434)+TX,Dimehypo (803)+TX,Desinsection double sodium salt (803)+TX,Su Li rhzomorphs (alias) [CCN]+TX,Tolfenpyrad (809)+TX,Tralomethrin (812)+TX,Transfluthrin (813)+TX,Anti- Permethrin (1440)+TX,Triamiphos (1441)+TX,Triaguron (818)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Metrifonate (824)+TX,Trichloromethyl 1605-3 (trich1ormetaphos-3) (alias) [CCN]+TX,Trichloronate (1452)+TX,The phosphorus of chlorobenzene second third (1455)+TX,Triflumuron (835)+TX,Landrin (840)+TX,Triprene (1459)+TX,Vamidothion (847)+TX,Fluorine pyrazoles worm [CCN]+TX,Veratridine (alias) (725)+TX,Jervine (alias) (725)+TX,XMC(853)+TX,Meobal (854)+TX,YI-5302 (compound code)+TX,ζ-cypermethrin (205)+TX,Zetamethrin (alias)+TX,Zinc phosphide (640)+TX,Zolaprofos (1469) and ZXI8901 (research code) (858)+TX,
It is selected from the group the invertebrate poison of material：Two (tributyl tin) oxide (IUPAC titles) (913)+TX, acetbromamide [CCN]+TX, calcium arsenate [CCN]+TX, cloethocarb (999)+TX, Paris green [CCN]+TX, copper sulphate (172)+TX, fentin (347)+TX, ferric phosphate (IUPAC titles) (352)+TX, the methaldehyde (518)+TX, methiocarb (530)+TX, niclosamide (576)+TX, niclosamide ethanolamine salt (576)+TX, pentachlorophenol (623)+TX, pentachlorobenzene sodium oxide molybdena (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, Butinox (913)+TX, trifenmorph (1454)+TX, Landrin (840)+TX, fentin acetate (IUPAC titles) (347) and fentin hydrochloride (IUPAC titles) (347)+TX,
It is selected from the group the nematicide of material：AKD-3088 (compound code)+TX,1,The bromo- 3- chloropropanes of 2- bis- (IUPAC/ chemical abstracts name) (1045)+TX,1,2- dichloropropanes (IUPAC/ chemical abstracts name) (1062)+TX,With 1,The 1 of 3- dichloropropylenes,2- dichloropropanes (IUPAC titles) (1063)+TX,1,3- dichloropropylenes (233)+TX,3,4- dichloros thiophane 1,1- dioxide (IUPAC/ chemical abstracts name) (1065)+TX,3- (4- chlorphenyls) -5- methyl rhodanine (IUPAC titles) (980)+TX,5- methyl -6- thio -1,3,5- thiadiazine alkane -3- guanidine-acetic acids (IUPAC titles) (1286)+TX,6- isopentene groups adenine phosphate (alias) (210)+TX,AVM (1)+TX,Acetyl worm nitrile [CCN]+TX,Alanycarb (15)+TX,Aldicarb (16)+TX,Aldoxycarb (863)+TX,AZ60541 (compound code)+TX,benclothiaz[CCN]+TX,Benomyl (62)+TX,(alias)+TX,Cadusafos (109)+TX,Carbofuran (118)+TX,Carbon disulfide (945)+TX,Carbosulfan (119)+TX,Chloropicrin (141)+TX,Chlopyrifos (145)+TX,Cloethocarb (999)+TX,The basic element of cell division (alias) (210)+TX,Dazomet (216)+TX,DBCP(1045)+TX,DCIP(218)+TX,Nellite (1044)+TX,Dichlofenthion (1051)+TX,Dicliphos (alias)+TX,Rogor (262)+TX,Doractin (alias) [CCN]+TX,Emaricin (291)+TX,Emaricin benzoic ether (291)+TX,According to general rhzomorph (alias) [CCN]+TX,Phonamiphos (312)+TX,Bromofume (316)+TX,Fenamiphos (326)+TX,Tebufenpyrad (alias)+TX,Fensulfothion (1158)+TX,Lythidathion (408)+TX,Fosthietan (1196)+TX,Furfural (alias) [CCN]+TX,GY-81 (research code) (423)+TX,Speed kills sulphur phosphorus [CCN]+TX,Iodomethane (IUPAC titles) (542)+TX,isamidofos(1230)+TX,Isazofos (1231)+TX,Olivomitecidin (alias) [CCN]+TX,Chaff adenine phosphate (alias) (210)+TX,Mecarphon (1258)+TX,Hundred mu of (519)+TX,Hundred mu-sylvite (alias) (519)+TX,Hundred mu-sodium salt (519)+TX,Bromomethane (537)+TX,Methyl-isorhodanate (543)+TX,Polynactin oxime (alias) [CCN]+TX,Moxidectin (alias) [CCN]+TX,Myrothecium verrucaria component (alias) (565)+TX,NC-184 (compound code)+TX,Oxamyl (602)+TX,Thimet (636)+TX,Phosphamidon (639)+TX,Phosphorus worm prestige [CCN]+TX,Cadusafos (alias)+TX,Selamectin (alias) [CCN]+TX,Pleocidin (737)+TX,Terbam (alias)+TX,Terbufos (773)+TX,Penphene (IUPAC/ chemical abstracts name) (1422)+TX,Thiafenox (alias)+TX,Thionazin (1434)+TX,Hostathion (820)+TX,Triazuron (alias)+TX,Xylenols [CCN]+TX,YI-5302 (compound code) and zeatin (alias) (210)+TX,
It is selected from the group the nitrification inhibitor of material：Ehtyl potassium xanthate [CCN] and trichloromethyl pyridine (580)+TX,
It is selected from the group the plant activator of material：Thiadiazoles element (6)+TX, thiadiazoles element-S- methyl (6)+TX, probenazole (658) and big Gentrin Knotweed P.E (alias) (720)+TX,
It is selected from the group the rat poison of material：2- isovaleryl indane -1,3- diketone (IUPAC titles) (1246)+TX,4- (quinoxaline -2- bases amino) benzsulfamide (IUPAC titles) (748)+TX,α-chloropharin [CCN]+TX,Aluminum phosphate (640)+TX,ANTU (880)+TX,Arsenic trioxide (882)+TX,Barium carbonate (891)+TX,Double mouse urea (912)+TX,Brodifacoum (89)+TX,Bromadiolone (91)+TX,Bromethalin (92)+TX,Cyanogas (444)+TX,Chloralose (127)+TX,Chloradion (140)+TX,Vitamin D3 (alias) (850)+TX,Coumachlor (1004)+TX,Coumafuryl (1005)+TX,Coumatetralyl (175)+TX,Crimidine (1009)+TX,Difenacoum (246)+TX,Difethialone (249)+TX,Diphacinone (273)+TX,Ergocalciferol (301)+TX,Flocoumafen (357)+TX,Fluorakil 100 (379)+TX,Flupropadine (1183)+TX,Flupropadine hydrochloride (1183)+TX,γ-HCH(430)+TX,HCH(430)+TX,Hydrogen cyanide (444)+TX,Iodomethane (IUPAC titles) (542)+TX,Lindane (430)+TX,Magnesium phosphide (IUPAC titles) (640)+TX,Bromomethane (537)+TX,Shoxin (1318)+TX,Malicious mouse spirit (1336)+TX,Hydrogen phosphide (IUPAC titles) (640)+TX,Phosphorus [CCN]+TX,Duocide (1341)+TX,Potassium arsenite [CCN]+TX,Pyrinuron (1371)+TX,Red squill (1390)+TX,Sodium arsenite [CCN]+TX,Cymag (444)+TX,Fratol (735)+TX,Strychnine (745)+TX,Thallium sulfate [CCN]+TX,Warfarin (851) and zinc phosphide (640)+TX,
It is selected from the group the synergist of material：2- (2- Butoxyethoxies) ethyl pepper base ester (IUPAC titles) (934)+TX, 5- (1, 3- benzodioxole -5- bases) -3- hexyl hexamethylene -2- ketenes (IUPAC titles) (903)+TX, fanesol (alias) (324)+TX with nerolidol, MB-599 (research code) (498)+TX, MGK264 (research code) (296)+TX, Butacide (649)+TX, Piprotal (1343)+TX, propyl isome (1358)+TX, S421 (research code) (724)+TX, Safroxan (1393)+TX, sesamolin (1394) and sulfoxide (1406)+TX,
It is selected from the group the animal repellant of material：Anthraquinone (32)+TX, chloralose (127)+TX, copper naphthenate [CCN]+TX, Cupravit (171)+TX, diazinon (227)+TX, bicyclopentadiene (chemical name) (1069)+TX, Guanoctine (422)+TX, biguanides acetate (422)+TX, methiocarb (530)+TX, pyridine -4- amine (IUPAC titles) (23)+TX, thiram (804)+TX, Landrin (840)+TX, zinc naphthenate [CCN] and ziram (856)+TX
It is selected from the group the virucide of material：Imanin (alias) [CCN] and virazole (alias) [CCN]+TX,
And it is selected from the group the wound protective agent of material：Mercury oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX,
Formula A-1 compounds
Formula A-2 compounds
Formula A-3 compounds
Formula A-4 compounds
Formula A-5 compounds
Formula A-6 compounds
Formula A-7 compounds
Formula A-8 compounds
Formula A-9 compounds
Formula A-10 compounds
Formula A-11
Formula A-12
Formula A-13
Formula A-14
Formula A-15
Formula A-16
Formula A-17
Formula A-18
Formula A-19
Formula A-20
Formula A-21
Formula A-22
Formula A-23
Formula A-24
Formula A-25
Formula A-26
With oxygen ring azoles (60207-31-0)+TX,Bitertanol [70585-36-3]+TX,Bromuconazole [116255-48-2]+TX,Cyproconazole [94361-06-5]+TX,Difenoconazole [119446-68-3]+TX,Olefin conversion [83657-24-3]+TX,Epoxy bacterium azoles [106325-08-0]+TX,RH-7592 [114369-43-6]+TX,Fluquinconazole [136426-54-5]+TX,Flusilazole [85509-19-9]+TX,Flutriafol [76674-21-0]+TX,Hexaconazole [79983-71-4]+TX,Imazalil [35554-44-0]+TX,Glyoxalin [86598-92-7]+TX,Kind bacterium azoles [125225-28-7]+TX,Metconazole [125116-23-6]+TX,Nitrile bacterium azoles [88671-89-0]+TX,Pefurazoate [101903-30-4]+TX,Penconazole [66246-88-6]+TX,Prothioconazoles [178928-70-6]+TX,Pyrifenox [88283-41-4]+TX,Prochloraz [67747-09-5]+TX,Propiconazole [60207-90-1]+TX,Simeconazoles [149508-90-7]+TX,Tebuconazole [107534-96-3]+TX,Tetraconazole [112281-77-3]+TX,Triazolone [43121-43-3]+TX,Triadimenol [55219-65-3]+TX,Fluorine bacterium azoles [99387-89-0]+TX,Triticonazole [131983-72-7]+TX,Ancymidol [12771-68-5]+TX,Fenarimol [60168-88-9]+TX,Nuarimol [63284-71-9]+TX,Bupirimate [41483-43-6]+TX,Dimethirimol [5221-53-4]+TX,Ethirimol [23947-60-6]+TX,Dodemorph [1593-77-7]+TX,Fenpropidin [67306-00-7]+TX,Third bacterium spirit [67564-91-4]+TX,Volution bacterium amine [118134-30-8]+TX,Tridemorph [81412-43-3]+TX,Cyprodinil [121552-61-2]+TX,Mepanipyrim [110235-47-7]+TX,Pyrimethanil [53112-28-0]+TX,Fenpiclonil [74738-17-3]+TX,Fludioxonil [131341-86-1]+TX,M 9834 [71626-11-4]+TX,Furalaxyl [57646-30-7]+TX,Metalaxyl [57837-19-1]+TX,R- metalaxyls [70630-17-0]+TX,Ofurace [58810-48-3]+TX,Wakil [77732-09-3]+TX,Benomyl [17804-35-2]+TX,Carbendazim [10605-21-7]+TX,Debacarb [62732-91-6]+TX,Furidazol [3878-19-1]+TX,Probenazole [148-79-8]+TX,Chlozolinate [84332-86-5]+TX,Sclex [24201-58-9]+TX,Iprodione [36734-19-7]+TX,Myclozolin [54864-61-8]+TX,Procymidone [32809-16-8]+TX,Vinclozolin [50471-44-8]+TX,Niacinamide [188425-85-6]+TX,Carboxin [5234-68-4]+TX,Fenfuram [24691-80-3]+TX,Flutolanil [66332-96-5]+TX,Mebenil [55814-41-0]+TX,Oxycarboxin [5259-88-1]+TX,Pyrrole metsulfovax [183675-82-3]+TX,Thiophene fluorine bacterium amine [130000-40-7]+TX,Guanoctine [108173-90-6]+TX,Dodine [2439-10-3] [112-65-2] (freieBase)+TX,Iminoctadine [13516-27-3]+TX,Fluoxastrobin [131860-33-8]+TX,Dimoxystrobin [149961-52-4]+TX,Enestroburin { Proc.BCPC,Int.Congr.,Glasgow,2003,1+TX,93}+TX,Fluoxastrobin [361377-29-9]+TX,Kresoxim-methyl [143390-89-0]+TX,SSF 126 [133408-50-1]+TX,Trifloxystrobin [141517-21-7]+TX,Orysastrobin [248593-16-0]+TX,ZEN 90160 [117428-22-5]+TX,Pyraclostrobin [175013-18-0]+TX,Fervam [14484-64-1]+TX,Mancozeb [8018-01-7]+TX,Maneb [12427-38-2]+TX,Carbatene [9006-42-2]+TX,Propineb [12071-83-9]+TX,Thiram [137-26-8]+TX,Zineb [12122-67-7]+TX,Ziram [137-30-4]+TX,Difoltan [2425-06-1]+TX,Captan [133-06-2]+TX,Dichlofluanid [1085-98-9]+TX,Fluoromide [41205-21-4]+TX,Folpet [133-07-3]+TX,Tolylfluanid [731-27-1]+TX,Bordeaux mixture [8011-63-0]+TX,Kocide SD [20427-59-2]+TX,Cupravit [1332-40-7]+TX,Copper sulphate [7758-98-7]+TX,Cupric oxide [1317-39-1]+TX,Mancopper [53988-93-5]+TX,Copper 8-hydroxyquinolinate [10380-28-6]+TX,Dinitro ester [131-72-6]+TX,Nitrothalisopropyl [10552-74-6]+TX,Edifenphos [17109-49-8]+TX,Different rice blast net [26087-47-8]+TX,Isoprothiolane [50512-35-1]+TX,Phosdiphen [36519-00-3]+TX,Pyrazophos [13457-18-6]+TX,Tolelofos-methyl [57018-04-9]+TX,Acibenzolar [135158-54-2]+TX,Anilazine [101-05-3]+TX,Benzene metsulfovax [413615-35-7]+TX,Blasticidin S [2079-00-7]+TX,Chinomethionat [2439-01-2]+TX,Chloroneb [2675-77-6]+TX,Bravo [1897-45-6]+TX,Cyflufenamid [180409-60-3]+TX,Cymoxanil [57966-95-7]+TX,Dichlone [117-80-6]+TX,Double chlorine zarilamid [139920-32-4]+TX,Diclomezin [62865-36-5]+TX,Botran [99-30-9]+TX,Diethofencarb [87130-20-9]+TX,Dimethomorph [110488-70-5]+TX,SYP-LI90 (flumorph) [211867-47-9]+TX,Dithianon [3347-22-6]+TX,Guardian [162650-77-3]+TX,Grandox fumigant [2593-15-9]+TX,Famoxate [131807-57-3]+TX,Fenamidone [161326-34-7]+TX,Zarilamid [115852-48-7]+TX,Fentin [668-34-8]+TX,Ferimzone [89269-64-7]+TX,Fluazinam [79622-59-6]+TX,Fluopicolide [239110-15-7]+TX,Flusulfamide [106917-52-6]+TX,Fenhexamid [126833-17-8]+TX,Aliette [39148-24-8]+TX,Hymexazol [10004-44-1]+TX,Iprovalicarb [140923-17-7]+TX,IKF-916 (cyazofamid) [120116-88-3]+TX,Kasugarnycin [6980-18-3]+TX,Methasulfocarb [66952-49-6]+TX,Table metrafenone (Metrafenone) [220899-03-6]+TX,Pencycuron [66063-05-6]+TX,Rabcide [27355-22-2]+TX,Polyoxin [11113-80-7]+TX,Probenazole [27605-76-1]+TX,Propamocarb [25606-41-1]+TX,The third oxygen quinoline (Proquinazid) [189278-12-4]+TX,Pyroquilon [57369-32-1]+TX,Quinoxyfen [124495-18-7]+TX,Pentachloronitrobenzene [82-68-8]+TX,Sulphur (Schwefel) [7704-34-9]+TX,Tiadinil (Tiadinil) [223580-51-6]+TX,Triazoxide [72459-58-6]+TX,Tricyclazole [41814-78-2]+TX,Triforine [26644-46-2]+TX,Valida [37248-47-8]+TX,Zoxamide (RH7281) [156052-68-5]+TX,Mandipropamid (Mandipropamid) [374726-62-2]+TX,Formula F-1 compounds
Wherein Ra5It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, formula F-2 compounds
Wherein Ra6It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, formula F-3 racemic compound (cis)
Wherein Ra7It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-4 racemic compound (trans)
Wherein Ra7It is trifluoromethyl or difluoromethyl (W02004/035589)+TX, formula F-5 compounds
This is the epimeric mixture of formula F-3 (cis) and F-4 (trans) racemic compound, and the ratio of wherein formula F-3 (cis) racemic compounds and formula F-4 (trans) racemic compound is 1000：1 to 1：1000, wherein Ra7It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-6 compounds
Wherein Ra8It is trifluoromethyl or difluoromethyl (WO2004/035589)+TX, formula F-7 racemic compound (trans)
Wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-8 racemic compound (cis)
Wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-9 compounds
This is the mixture of formula F-7 (trans) and F-8 (cis) racemic compound, and the ratio of wherein formula F-7 (trans) racemic compounds and formula F-8 (cis) racemic compound is 2：1 to 100：1, wherein Ra9It is trifluoromethyl or difluoromethyl (WO03/074491)+TX,
Formula F-10 compounds
Wherein R10It is trifluoromethyl or difluoromethyl (WO2004/058723)+TX, formula F-11 racemic compound (trans)
Wherein R11It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-12 racemic compound (cis)
Wherein R11It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, formula F-13 compounds
This is formula F-11 (trans) and F-12 (cis) racemic mixture, wherein R11It is trifluoromethyl or difluoromethyl (WO03/074491)+TX, and formula F-14 compounds
(WO2004/058723)+TX, and formula F-15 compounds
The compound of formula I selected from table T1 to T43 and the mixed proportion of active component as described above that the mixture of compound of formula I and active component as described above selected from table T1 to T43 is included are preferably 100：1 to 1：6000, especially 50：1 to 1：50 more particularly 20：1 to 1：20, or even more particularly 10：1 to 1：10, particularly 5：1 and 1：5, particularly preferred 2：1 to 1：2 ratio, 4：1 to 2：1 be also also, it is preferred that ratio, most important ratio is 1：1 or 5：1 or 5：2 or 5：3 or 5：4 or 4：1 or 4：2 or 4：3 or 3：1 or 3：2 or 2：1 or 1：5 or 2：5 or 3：5 or 4：5 or 1：4 or 2：4 or 3：4 or 1：3 or 2：3 or 1：2 or 1：600 or 1：300 or 1：150 or 1：35 or 2：35 or 4：35 or 1：75 or 2：75 or 4：75 or 1：6000 or 1：3000 or 1：1500 or 1：350 or 2：350 or 4：350 or 1：750 or 2：750 or 4：750.These mixed proportions should be read to include, on the one hand, weight ratio, and on the other hand, also including mol ratio.
Mixture containing the compound of formula I selected from table T1 to T43 and one or more as described above active components can be for example with individually " i.e. with " form, merging spraying mixture form such as " tank mix " to be made up of single active component separate formulation, and applied in the mode that is applied in combination of single component continuous administration, the continuous administration is to apply successively in interval rational short cycle such as a few houres or several days.It is not the key for implementing the present invention using the compound of formula I selected from table T1 to T43 and the order of active component as described above.
Index in the right square bracket of active component, such as [3878-19-1] refer to chemical abstracts registry no.Formula A-1 is described in WO03/015518 or WO04/067528 to A-26 compounds.Above-mentioned mixing pairing composition is known.Wherein active component is included in " The PesticideManual " (agricultural chemicals handbook) [The Pesticide Manual-A World Compendium；13rd edition；Editor：C.D.S.Tomlin；The British Crop ProtectionCouncil] in, they are described with the numbering gone out given in the round parentheses of specific compound above wherein；Such as compound " AVM " is described with numbering (1).Wherein " [CCN] " is added for specific compound above, described compound is included in that " in Compendiumof Pesticide Common Names " (agricultural chemicals common name summary), they can be in Internet [A.Wood；Compendium of Pesticide Common Names, Copyright
1995-2004] in find；For example, compound " acetyl worm nitrile (acetoprole) " is described in the Internet addresshttp:In //www.alanwood.net/pesticides/acetoprole.html..
Most active components are represented by above so-called " common name ", and corresponding " ISO common names " or other " common name " is used in different situations.If its title is not " common name ", title that used title species goes out given in the round parentheses with specific compound is replaced；In this case, using IUPAC titles, IUPAC/ chemical abstracts name, " chemical name ", " traditional title ", " chemical combination name " or " research code ", if or both without using above-mentioned specified title or without using " common name ", use alias." CAS registration numbers " represents chemical abstracts registry no.
Biological Examples(%=percentage by weights, unless otherwise indicated)
Embodiment B1：To Spodoptera littoralis (Spodoptera littoralis) activity
Cotton leaf disk is placed on the agar in the titer plate of 24- holes, sprayed with test solution.After drying, by the leaf disc 5L1Larval infestation.3 days (DAT) after processing, checks the death rate, repellent effect, trophic behaviour and the growth regulating of sample.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.1, T15.1.91, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T16.1.1, T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T16.1.91, T13.1.92, T13.1.361, T13.1.391, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.93, T13.1.113, T13.1.21, T13.1.111 has the activity (400ppm) more than 80%.
Embodiment B2：To tobacco budworm (Heliothis virescens) activity
Ovum (0-24 hours ages) is placed on the artificial food of 24- holes titer plate, handled by pipetting with test solution.After the incubation period of 4 days, egg mortality, larval mortality and the growth regulating of sample are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.1, T15.1.91, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T16.1.1, T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T16.1.91, T13.1.92, T13.1.361, T13.1.391, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.93, T13.1.113, T13.1.21, T13.1.111 has the activity (400ppm) more than 80%.
Embodiment B3：To diamondback moth (P1ute1la xyloste1la) activity
The artificial food of 24- hole titer plates (MTP) is handled with test solution by pipetting.After drying, the MTP titer plates are infected with larva (L2) (10-15/ holes).After the incubation period of 5 days, larval mortality, food refusal behavior and the growth regulating of sample are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.1, T15.1.91, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T16.1.1, T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T16.1.91, T13.1.92, T13.1.361, T13.1.391, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.93, T13.1.113, T13.1.21, T13.1.111 has the activity (400ppm) more than 80%.
Embodiment B4：To the activity with spot cucumber chrysomelid (Diabrotica balteata)
The artificial food of 24- hole titer plates (MTP) is handled with test solution by pipetting.After drying, the MTP titer plates are infected with larva (L2) (6-10/ holes).After the incubation period of 5 days, larval mortality, food refusal behavior and the growth regulating of sample are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.1, T15.1.91, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T16.1.91, T13.1.92, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.113, T13.1.21, T13.1.111 are with the activity (400ppm) more than 80%.
Embodiment B5：To black peach aphid (Myzus persicae) activity：(contact toxicity)
On the agar that sunflower leaf disk is placed in 24- holes titer plate, sprayed with test solution.After drying, the leaf disc is infected with mixed age aphis population.After the incubation period of 6 days (DAT), the death rate and special-effect (such as phytotoxicity) of sample are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.91, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T13.1.92, T13.1.91, T13.1.96, T13.1.21 are with the activity (400ppm) more than 80%.
Embodiment B6：To black peach aphid (Myzuspersicae) activity：(systemic activity)
The root of pea seedling is infected with mixed age aphis population, is directly placed in test solution.After introducing 6 days, the sample death rate and the special-effect to plant are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T13.1.92, T13.1.6, T13.1.96, T13.1.93, T13.1.113, T13.1.21 are with the activity (400ppm) more than 80%.
Embodiment B7：To onion thrips (Thrips tabaci) activity：
Sunflower leaf disk is placed on the agar in the titer plate of 24- holes, sprayed with test solution.After drying, the leaf disc is infected with mixed age thrips population.After the incubation period of 6 days (DAT), the death rate and special-effect (such as phytotoxicity) of sample are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.91, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T16.1.91, T13.1.92, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.93, T13.1.113, T13.1.21, T13.1.111 are with the activity (400ppm) more than 80%.
Embodiment B8：To Tetranychus urticae (Tetranychus urticae) activity：
Kidney bean leaf disk is placed on the agar in the titer plate of 24- holes, sprayed with test solution.After drying, the leaf disc is infected with mixed age tetranychid population.After 8 days, egg mortality, larval mortality and the adult mortality of leaf disc are checked.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T9.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T13.1.21 have the activity (400ppm) more than 80%.
Embodiment B9：Absorbability to Spodoptera littoralis (Spodoptera littoralis) is killed
Worm agent is tested：
The corn seedling (maize (Zea mais), kind Stoneville) in 4 day age is placed in single bottle, the bottle contains 24ml water, and its Chinese medicine is diluted to 12.5ppm.Allow growth of seedling 6 days.Then, shearing blade, is placed in Petri dish (5cm diameters), and with 12-15, only 1 age Spodoptera littoralis larva is inoculated with, and 4 days (25 DEG C, 50%r.h., 18 of culture in growth room：6L：D illumination periods).Surviving insects number is counted, per cent death loss is calculated.Experiment repeats once.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T13.1.2, T15.1.1, T13.1.1, T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T17.1.2 (diastereoisomer B), T13.1.92, T13.1.361, T13.1.391, T13.1.91, T13.1.6, T13.1.96, T44.1.2, T13.1.8, T13.1.23, T13.1.113 are with the activity (400ppm) more than 80%.
Embodiment B10：To carpocapsa pononella (Cydiapomonella) activity：
The carpocapsa pononella serving piece (1.5cm is wide) of standard is through on bayonet, is immersed in atoleine (about 80 DEG C).After paraffin coating is hardened, the aqueous emulsion containing 400ppm active components is applied with De Vilbis sprayers (25ml, 1 bar).After layer of spraying is dried, the square is put into plastic containers, two carpocapsa pononellas just hatched (1 instar larvae) are migrated afterwards.Then, the container is closed with vinyl cover.At 26 DEG C with after 40-60% relative humidity culture 14 days, the survival rate of caterpillar and their growth regulating are determined.
In this experiment, compound listed in above-mentioned table shows good activity.Especially compound T9.1.2 (diastereoisomer A), T9.1.2 (diastereoisomer B), T17.1.2 (diastereoisomer A), T13.1.92 have the activity (400ppm) more than 80%.
Embodiment B11：The compounds of this invention and contrast closest in structure in the prior art
The desinsection of compound (WO2003/015518, the compound N described by page 108 is o.296) is lived
Property compares：
The corn seedling (maize (Zea mais), kind Stoneville) in 4 day age is placed in single bottle, the bottle contains 24ml water, and its Chinese medicine is diluted to predetermined concentration (3 and 0.8ppm).Allow growth of seedling 6 days.Then, shearing blade, is placed in Petri dish (3.5cm diameters), and with 12-15, only 1 age Spodoptera littoralis larva is inoculated with, and 4 days (25 DEG C, 50%r.h., 18 of culture in growth room：6L：D illumination periods).Surviving insects number is counted, per cent death loss is calculated.The effect adjusted to larval growth is compared with described compare.Calculate larval growth reduction percentage.Test repeats once.As a result it is shown in table B11：
Table B11：For Spodoptera littoralis (Lepidoptera：Noctuidae) absorbability desinsection test：
| Compound： | Concentration (ppm) | Death after 4 days Rate (%) | Larval growth drops (% with to shining into Row compares) |
| Comp.296 (prior art) | 3 | 0 | 0 |
| Comp.296 (prior art) | 0.8 | 0 | 0 |
| Comp.T13.1.391 (present invention) | 3 | 55 | 100 |
| Comp.T13.1.391 (present invention) | 0.8 | 10 | 0 |
Table B11 shows the compound phase ratio with prior art, and compound N o.T13.1.391 of the invention has substantially more excellent insecticidal action to Spodoptera littoralis.Especially under 3ppm rate of application, compound of the invention is much more excellent than the prior art compound.Based on the similitude on these compound structures, this effect improved is not expected.
Claims (4)
1. Formulas I a compounds
Wherein
R91It is C1-C4Alkyl or halogen；
R92It is halogen or cyano group；
R93It is halogen, C1-C4Haloalkyl or C1-C4Halogenated alkoxy；
A is N- benzyls, SO or SO2；
R34It is hydrogen or C1-C4Alkyl；
M is 0,1,2,3 or 4；With
R35It is hydrogen or C1-C4Alkyl,
And agriculturally acceptable salt/isomers/diastereoisomer/enantiomter/dynamic isomer/N- oxides of these compounds.
2. Formula VIII compound
Wherein R3、R34And R35It is hydrogen, m is 0,1,2,3 or 4；And q is 1.
3. composition pesticide, its comprising at least one Formulas I a compounds according to claim 1 in all cases for available salt form on free form or agricultural chemicals or, if appropriate, its dynamic isomer is used as active component and at least one auxiliary agent.
4. controlling the method for insect, this method includes composition according to claim 3 being applied to the insect or their environment.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06000826 | 2006-01-16 | ||
| EP06000826.5 | 2006-01-16 | ||
| EP06002803 | 2006-02-13 | ||
| EP06002803.2 | 2006-02-13 | ||
| PCT/EP2007/000302 WO2007080131A2 (en) | 2006-01-16 | 2007-01-15 | Anthranilamide derivatives and their use for the control of insects and acari |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101394742A CN101394742A (en) | 2009-03-25 |
| CN101394742B true CN101394742B (en) | 2012-05-23 |
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| ZA (1) | ZA200805502B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012500782A (en) * | 2008-08-22 | 2012-01-12 | シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト | Insecticidal compounds |
| MA33372B1 (en) * | 2009-06-22 | 2012-06-01 | Syngenta Participations Ag | Pesticide compounds |
| CN103649070B (en) * | 2011-07-08 | 2016-05-18 | 先正达参股股份有限公司 | For the preparation of the method for thia ring butylamine |
| WO2014135588A1 (en) * | 2013-03-06 | 2014-09-12 | Bayer Cropscience Ag | Alkoximino-substituted anthranilic acid diamides as pesticides |
| CN113367118A (en) * | 2021-05-14 | 2021-09-10 | 中国农业科学院上海兽医研究所(中国动物卫生与流行病学中心上海分中心) | Application of Chinese cinnamon essential oil |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419537A (en) * | 2000-03-22 | 2003-05-21 | 纳幕尔杜邦公司 | Insecticidal anthranilamides |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1419537A (en) * | 2000-03-22 | 2003-05-21 | 纳幕尔杜邦公司 | Insecticidal anthranilamides |
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| ZA200805502B (en) | 2009-10-28 |
| CN101394742A (en) | 2009-03-25 |
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